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Tailored synthesis of complexes and polymers containing organoiron and organocobalt Winram, Diana Joyce 2010

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    Tailored Synthesis of Complexes and Polymers Containing Organoiron and Organocobalt   by   Diana Joyce Winram      A THESIS SUBMITTED Iglyph1197 PARTIAL FULFILLMEglyph1197T OF THE REQUIREMEglyph1197TS FOR THE DEGREE OF    Master of Science   in   The College of Graduate Studies   (Chemistry)     THE Uglyph1197IVERSITY OF BRITISH COLUMBIA (Okanagan)    Febuary 2010   ©Diana Joyce Winram 2010 ii  Abstract This thesis describes synthetic strategies for the incorporation of organoiron and organocobalt into polymers.  Norbornene and methacrylate based polymers which contained µ-alkyne-bis(tricarbonylcobalt) complexes and either η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate or ferrocene moieties were synthesized.  Norbornene monomers which contained both the organoiron and the organocobalt complexes were successfully polymerized using ring opening metathesis polymerization.  Radical polymerization of methacrylate monomers which contained η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate moieties and alkyne functional groups, allowed for the coordination of dicobalt hexacarbonyl post polymerization.  The monomers and their precursors were characterized through nuclear magnetic resonance spectroscopy, infrared spectroscopy and cyclic voltammetry.  The molecular weights of the polymers were estimated using gel permeation chromatography and the thermal properties were studied with thermogravimetric analysis and differential scanning calorimetry.  Another class of organoiron monomers containing alkyne functional groups were polymerized through condensation of their η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate moieties with various dithiols.  A monomer which contained both η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate and µ-alkyne-bis(tricarbonylcobalt) moieties was also combined with various dithiol linking groups.  Preliminary studies on the synthesis and characterization of three siloxane based polymers which contained η6-(arene)-η5-cyclopentadienyliron(II) hexafluorophosphate moieties were also explored.   iii  Table of Contents Abstract .......................................................................................................................................... ii Table of Contents ......................................................................................................................... iii List of Tables .............................................................................................................................. viii List of Figures ............................................................................................................................... ix List of Schemes ........................................................................................................................... xiii List of Symbols and Abbreviations ........................................................................................... xv Acknowledgements .................................................................................................................. xviii Chapter 1: Introduction ............................................................................................................... 1 1.1 The chemistry of ferrocene ................................................................................................... 1 1.2 The synthesis and chemistry of η6-(arene)-η5-cyclopentadienyliron(II) hexafluorophosphate complexes ................................................................................................. 4 1.3 Synthesis and chemistry of µ-alkyne-bis(tricarbonylcobalt) complexes .............................. 9 1.4 Metal containing polymers.................................................................................................. 10 1.5 Scope of the present work ................................................................................................... 11 1.6 Materials and instrumentation ............................................................................................. 12 Chapter 2: glyph1197orbornene based polymers ................................................................................... 14 2.1 Introduction ......................................................................................................................... 14 2.2 Synthesis and characterization of polynorbornenes containing organoiron and cobalt carbonyl ..................................................................................................................................... 17 2.2.1 Synthesis of a norbornene monomer containing ferrocene .......................................... 17 2.2.2 Polymerization of a norbornene monomer containing ferrocene................................. 27 2.2.3 Synthesis of a norbornene monomer containing both ferrocene and cobalt ................ 28 iv  2.2.4 Polymerization of a norbornene monomer containing both ferrocene and cobalt ....... 35 2.3 Synthesis and characterization of η6-arene-η5-cyclopentadienyliron(II) and cobalt containing polynorbornenes ...................................................................................................... 37 2.3.1 Synthesis of a norbornene monomer containing alkyne-hexacarbonyl cobalt and two η6-chloroarene-η5-cyclopentadienyliron(II) moieties ........................................................... 37 2.3.2 Polymerization of a norbornene monomer containing cobalt carbonyl and two η6-arene-η5-cyclopentadienyliron(II) moieties .......................................................................... 49 2.3.3 Synthesis of a norbornene monomer containing a single η6-arene-η5-cyclopentadienyliron(II) moiety and cobalt carbonyl ........................................................... 53 2.3.4 Polymerization of norbornene monomer containing a single η6-arene-η5-cyclopentadienyliron(II) moiety and cobalt carbonyl ........................................................... 62 2.4 Molecular weight determination of polymers ..................................................................... 63 2.5 Thermal analysis of polymers ............................................................................................. 64 2.6 Cyclic voltammetry of norbornene complexes ................................................................... 66 2.7 Summary ............................................................................................................................. 67 2.8 Detailed experimental ......................................................................................................... 69 Chapter 3: Methacrylate based polymers ................................................................................. 83 3.1 Introduction ......................................................................................................................... 83 3.2 Synthesis and characterization of ferrocene and cobalt containing polymethacrylates ...... 87 3.2.1 Synthesis of a methacrylate monomer that contains ferrocene .................................... 87 3.2.2 Synthesis of a model methacrylate complex that contains both ferrocene and cobalt carbonyl ................................................................................................................................. 92 3.2.3 Polymerization of a ferrocene-containing methacrylate monomer .............................. 96 v  3.2.4 Coordination of cobalt carbonyl to a ferrocene-containing methacrylate polymer ..... 98 3.3 Synthesis and characterization of a polymethacrylate containing η6-arene-η5 -cyclopentadienyliron and cobalt carbonyl .............................................................................. 100 3.3.1 Synthesis of a methacrylate monomer containing two η6-arene-η5-cyclopentadienyliron(II) moieties ....................................................................................... 100 3.3.2 Polymerization of a methacrylate monomer containing two η6-arene-η5-cyclopentadienyliron(II) moieties ....................................................................................... 103 3.3.3 Coordination of cobalt carbonyl to a methacrylate polymer containing two η6-arene-η5-cyclopentadienyliron(II) moieties .................................................................................. 105 3.3.4 Synthesis of a methacrylate monomer containing a single η6-arene-η5-cyclopentadienyliron(II) moiety ......................................................................................... 108 3.3.5 Polymerization of a methacrylate monomer containing a single η6-arene-η5-cyclopentadienyliron(II) moiety ......................................................................................... 111 3.3.6 Coordination of cobalt carbonyl to a methacrylate polymer monomer containing a single η6-arene-η5-cyclopentadienyliron(II) moiety ........................................................... 113 3.4 Molecular weight determination of polymers ................................................................... 114 3.5 Thermal analysis of polymers ........................................................................................... 115 3.6 Summary ........................................................................................................................... 117 3.7 Detailed experimental ....................................................................................................... 118 Chapter 4: Condensation polymers ......................................................................................... 125 4.1 Introduction ....................................................................................................................... 125 4.2 Synthesis and characterization of condensation polymers containing η6-arene-η5-cyclopentadienyliron(II) and cobalt carbonyl ......................................................................... 128 vi  4.2.1 Synthesis of a monomer containing η6-arene-η5-cyclopentadienyliron(II) and alkyne moieties ............................................................................................................................... 128 4.2.2 Condensation polymerization of a monomer containing η6-arene-η5-cyclopentadienyliron(II) and alkyne moieties with dithiol linkers ..................................... 131 4.2.3 Coordination of cobalt carbonyl to a monomer containing η6-arene-η5-cyclopentadienyliron(II) and alkyne moieties..................................................................... 132 4.2.4 Condensation polymerization of a monomer containing η6-arene-η5-cyclopentadienyliron(II) and dicobalt hexacarbonyl moieties with dithiol linkers ............ 134 4.3 Thermal analysis of polymers ........................................................................................... 135 4.4 Cyclic voltammetry of complexes .................................................................................... 137 4.5 Summary ........................................................................................................................... 137 4.6 Detailed experimental ....................................................................................................... 138 Chapter 5: Preliminary work with polysiloxanes. ................................................................. 141 5.1 Introduction ....................................................................................................................... 141 5.2 Synthesis and characterization of polysiloxanes containing η6-arene-η5-cyclopentadienyliron ............................................................................................................... 143 5.2.1 Nucleophilic substitution of η6-halo-arene-η5-cyclopentadienyliron with       allylamine ............................................................................................................................ 143 5.2.2 Hydrosilation of allylamine complexes with methyldiethoxysilane .......................... 146 5.2.3 Cleavage of ethoxy groups from complexes 5.4 a-c .................................................. 149 5.2.4 Polymerization ........................................................................................................... 151 5.3 Thermal analysis of polymers ........................................................................................... 154 5.4 Cyclic voltammetry of complexes .................................................................................... 155 vii  5.5 Summary ........................................................................................................................... 156 5.6 Detailed experimental ....................................................................................................... 157 Chapter 6: General conclusions ............................................................................................... 161 Chapter 7: References .............................................................................................................. 163 Chapter 8: Appendices ............................................................................................................. 171 8.1 X-ray structure report for complex 2.6 ............................................................................. 171 8.2 X-ray structure report for complex 3.3 ............................................................................. 190 viii  List of Tables Table 2.1: Molecular weight data for polymers ............................................................................ 64 Table 2.2: Thermogravimetric analysis of polynorbornenes ........................................................ 65 Table 2.3: Differential scanning calorimetry of polynorbornenes ................................................ 66 Table 2.4: Cyclic voltammetric studies of norbornene complexes ............................................... 67 Table 3.1: Molecular weight data for polymers .......................................................................... 115 Table 3.2: Thermogravimetric analysis of polymermethacrylates ............................................. 116 Table 3.3: Differential scanning calorimetry of organoiron polymethacrylates ......................... 117 Table 4.1: Thermogravimetric analysis of polymers .................................................................. 136 Table 4.2: Differential scanning calorimetry of polymers .......................................................... 136 Table 4.3: Cyclic voltammetry of monomers ............................................................................. 137 Table 5.1: Thermogravimetric analysis of polymers 5.6 a-c ...................................................... 155 Table 5.2: Differential scanning calorimetry of polymers 5.6 a-c .............................................. 155 Table 5.3: Cyclic voltammetry of complexes ............................................................................. 156  ix  List of Figures Figure 1.1: Proposed structures for ferrocene ................................................................................. 1 Figure 1.2: The reactivity of ferrocene ........................................................................................... 2 Figure 1.3: Potentials for the oxidation states of ferrocene as determined by cyclic voltammetry.3 Figure 1.4: General synthesis for η6-(arene)-η5-cyclopentadienyliron(II) hexafluorophosphate complexes ....................................................................................................................................... 4 Figure 1.5: Reactivity of η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate salts.. 5 Figure 1.6: Nucleophilic aromatic substitution of a η6-(haloarene)-η5-cyclopentadienyliron(II) .. 6 Figure 1.7: Potentials for the oxidation states of η6-(hexamethylbenzene)-η5-cyclopentadienyliron(II) as determined by cyclic voltammetry ..................................................... 6 Figure 1.8: Proposed sequence for the photolysis of  η6-(arene)-η5-cyclopentadienyliron(II) complexes ....................................................................................................................................... 8 Figure 1.9: General synthesis of alkyne-cobalt carbonyl complexes.............................................. 9 Figure 2.1: Four strategies for norbornene polymerization .......................................................... 14 Figure 2.2: Ring opening metathesis of norbornene ..................................................................... 15 Figure 2.3: A few examples of polynorbornenes with η6-aryl-η5-cyclopentadienyliron(II) hexafluorophosphate groups in their side chain ............................................................................ 16 Figure 2.4: 1H NMR spectrum of compound 2.6 acetone-d6. ....................................................... 19 Figure 2.5: APT 13C NMR spectrum of compound 2.6 in CDCl3 ................................................. 20 Figure 2.6: ORTEP diagram of complex 2.6 ................................................................................ 21 Figure 2.7: 1H NMR spectrum of complex 2.8 in acetone-d6 ....................................................... 23 Figure 2.8: 1H NMR spectral comparison of complexes 2.6, 2.8 exo and 2.8 in acetone-d6 ........ 24 Figure 2.9: APT 13C NMR spectrum of complex 2.8 in acetone-d6 ............................................. 25 x  Figure 2.10: HMBC NMR spectrum of complex 2.8 in acetone-d6 ............................................. 26 Figure 2.11: HSQC NMR spectrum of complex 2.8 in acetone-d6 .............................................. 27 Figure 2.12: 1H NMR spectrum of complex 2.11 in acetone-d6 ................................................... 30 Figure 2.13: Expansion of the 1H NMR resonances in acetone-d6 of the methylenes next to the coordinated cobalt moieties of 2.11(exo/endo mixture) and 2.11 exo .......................................... 31 Figure 2.14: APT 13C NMR spectrum of complex 2.11 in acetone-d6 ......................................... 32 Figure 2.15: HSQC NMR spectrum of complex 2.11 in acetone-d6 ............................................ 33 Figure 2.16: HMBC NMR spectrum of complex 2.11 in acetone-d6 ........................................... 34 Figure 2.17: IR spectral comparison of complexes 2.8 and 2.11 .................................................. 35 Figure 2.18: 1H NMR spectrum of polymer 2.12 in CDCl3 .......................................................... 36 Figure 2.19: 1H NMR spectrum of complex 2.17 in acetone-d6 ................................................... 40 Figure 2.20: APT 13C NMR spectrum of complex 2.17 in acetone-d6 ......................................... 41 Figure 2.21: 1H NMR spectrum of complex 2.18 in acetone-d6 ................................................... 43 Figure 2.22: APT 13C NMR spectrum of complex 2.18 in acetone-d6 ......................................... 44 Figure 2.23: HSQC NMR spectrum of complex 2.18 in acetone-d6 ............................................ 45 Figure 2.24: HMBC NMR spectrum for complex 2.18 in acetone-d6 .......................................... 46 Figure 2.25: 1H NMR spectrum of complex 2.19 in acetone-d6 ................................................... 48 Figure 2.26: APT 13C NMR spectrum of complex 2.19 in acetone-d6 ......................................... 49 Figure 2.27: 1H NMR of polymer 2.20 in DMSO-d6 .................................................................... 52 Figure 2.28: 1H NMR spectrum of complex 2.23 in acetone-d6 ................................................... 55 Figure 2.29: APT 13C NMR spectrum of complex 2.23 in acetone-d6 ......................................... 56 Figure 2.30: 1H NMR spectrum of complex 2.24 in acetone-d6 ................................................... 58 Figure 2.31: APT 13C NMR spectrum of complex 2.24 in acetone-d6 ......................................... 59 xi  Figure 2.32: 1H NMR spectrum of complex 2.25 in acetone-d6 ................................................... 61 Figure 2.33: APT 13C NMR spectrum of complex 2.25 in acetone-d6 ......................................... 62 Figure 3.1: General polymerization of methacrylates ................................................................... 83 Figure 3.2: Initiation, propagation and termination of methylmethacrylate radical   polymerization .............................................................................................................................. 84 Figure 3.3: Production of radicals from AIBN ............................................................................. 85 Figure 3.4: Sample of methacrylates which contain organoiron moieties .................................... 86 Figure 3.5: 1H NMR spectrum of complex 3.2 in CDCl3 ............................................................. 88 Figure 3.6: 1H NMR spectral comparison for complexes 2.6 and 3.2 in CDCl3 .......................... 89 Figure 3.7: APT 13C NMR spectrum of complex 3.2 in CDCl3 ................................................... 90 Figure 3.8: HMBC NMR spectrum of complex 3.2 in CDCl3 ...................................................... 91 Figure 3.9: HSQC NMR spectrum of 3.2 in CDCl3 ..................................................................... 92 Figure 3.10: 1H NMR spectrum of complex 3.3 in acetone-d6 ..................................................... 94 Figure 3.11: APT 13C NMR spectrum of complex 3.3 in acetone-d6 ........................................... 95 Figure 3.12: ORTEP diagram for complex 3.3 ............................................................................. 96 Figure 3.13: 1H NMR spectrum of polymer 3.4 in CDCl3 ............................................................ 98 Figure 3.14: 1H NMR spectral comparison of polymers 3.4 and 3.5 in CDCl3 ............................ 99 Figure 3.15: 1H NMR spectrum of complex 3.7 in acetone-d6 ................................................... 102 Figure 3.16: APT 13C NMR spectrum of complex 3.7 in acetone-d6 ......................................... 103 Figure 3.17: 1H NMR spectrum of polymer 3.8 in acetone-d6 ................................................... 105 Figure 3.18: 1H NMR spectral comparison of polymers 3.8 and 3.9 in acetone-d6 .................... 108 Figure 3.19: 1H NMR spectrum of complex 3.10 acetone-d6 ..................................................... 110 Figure 3.20: APT 13C NMR spectrum of complex 3.10 in acetone-d6 ....................................... 111 xii  Figure 3.21: 1H NMR spectrum of polymer 3.11 ....................................................................... 113 Figure 4.1: Previously reported condensation polymers of η6-arene-η5-cyclopentadienyliron(II) hexafluorophosphate salts ........................................................................................................... 126 Figure 4.2: Previously reported condensation polymers of η6-arene-η5-cyclopentadienyliron(II) hexafluorophosphate salts ........................................................................................................... 127 Figure 4.3: 1H NMR spectrum of complex 4.1 in DMSO-d6 ...................................................... 129 Figure 4.4: APT 13C NMR spectrum of complex 4.1 in DMSO-d6 ............................................ 130 Figure 4.5: 1H NMR of complex 4.4 in DMSO-d6 ..................................................................... 133 Figure 4.6: APT 13C NMR spectrum of complex 4.4 in DMSO-d6 ............................................ 134 Figure 5.1: Hydrosilation of a terminal alkene ........................................................................... 142 Figure 5.2: Deprotonation of the amine group to form a zwitterion ........................................... 144 Figure 5.3: 1H NMR spectrum of complex 5.2 b in acetone-d6 .................................................. 145 Figure 5.4: APT 13C NMR spectrum of complex 5.2 b in acetone-d6 ........................................ 146 Figure 5.5: 1H NMR spectrum of complex 5.4 b in acetone-d6 .................................................. 148 Figure 5.6: APT 13C NMR spectrum of complex 5.4 b in acetone-d6 ........................................ 149 Figure 5.7: 1H NMR spectral visualization of the cleavage of the ethoxy groups from complex 5.4 b through a reaction with D2O in acetone-d6 ........................................................................151 Figure 5.8: 1H NMR spectrum of polymer 5.6 b in acetone-d6 .................................................. 153 Figure 5.9: APT 13C NMR spectrum of polymer 5.6 b in acetone-d6......................................... 154  xiii  List of Schemes Scheme 2.1: Synthesis of complex 2.4 ......................................................................................... 17 Scheme 2.2: Synthesis of complex 2.6 ......................................................................................... 18 Scheme 2.3: Synthesis of complex 2.8 ......................................................................................... 22 Scheme 2.4: Synthesis of complex 2.9 ......................................................................................... 28 Scheme 2.5: Synthesis of complex 2.11 ....................................................................................... 29 Scheme 2.6: Synthesis of polymer 2.12 ........................................................................................ 36 Scheme 2.7: Synthesis of complexes 2.14 a-c .............................................................................. 37 Scheme 2.8: Synthesis of complex 2.16 ....................................................................................... 38 Scheme 2.9: Synthesis of complex 2.17 ....................................................................................... 39 Scheme 2.10: Synthesis of complex 2.18 ..................................................................................... 42 Scheme 2.11: Synthesis of complex 2.19 ..................................................................................... 47 Scheme 2.12: Synthesis of polymer 2.20 ...................................................................................... 51 Scheme 2.13: Synthesis of complex 2.22 ..................................................................................... 53 Scheme 2.14: Synthesis of complex 2.23 ..................................................................................... 54 Scheme 2.15: Synthesis of complex 2.24 ..................................................................................... 57 Scheme 2.16: Synthesis of complex 2.25 ..................................................................................... 60 Scheme 2.17: Synthesis of polymer 2.26 ...................................................................................... 63 Scheme 3.1: Synthesis of complex 3.2 ......................................................................................... 87 Scheme 3.2: Synthesis of complex 3.3 ......................................................................................... 93 Scheme 3.3: Synthesis of polymer 3.4 .......................................................................................... 97 Scheme 3.4: Synthesis of polymer 3.5 .......................................................................................... 99 Scheme 3.5: Synthesis of complex 3.7 ....................................................................................... 101 xiv  Scheme 3.6: Synthesis of polymer 3.8 ........................................................................................ 104 Scheme 3.7: Synthesis of polymer 3.9 ........................................................................................ 107 Scheme 3.8: Synthesis of complex 3.10 ..................................................................................... 109 Scheme 3.9: Synthesis of polymer 3.11 ...................................................................................... 112 Scheme 3.10: Synthesis of polymer 3.12 .................................................................................... 114 Scheme 4.1: Synthesis of complex 4.1 ....................................................................................... 128 Scheme 4.2: Synthesis of polymers 4.3 a-c ................................................................................ 131 Scheme 4.3: Synthesis of complex 4.4 ....................................................................................... 132 Scheme 4.4: Synthesis of polymers 4.5 a-c ................................................................................ 135 Scheme 5.1: Synthesis of complexes 5.2 a-c .............................................................................. 143 Scheme 5.2: Synthesis of complexes 5.4 a-c .............................................................................. 147 Scheme 5.3: Cleavage of ethoxy groups from complexes 5.4 a-c .............................................. 150 Scheme 5.4: Synthesis of polymers 5.6 a-c ................................................................................ 152  xv  List of Symbols and Abbreviations  °C  Degrees Celsius 13C NMR Carbon 13 nuclear magnetic resonance spectroscopy 1H NMR Proton nuclear magnetic resonance spectroscopy APT  Attached proton test Ar  Aryl bp  Boiling point br.  broad calc.  calculated Cp  cyclopentadienyl ring cm  centimetres  δ  NMR chemical shift in parts per million downfield from a standard d  Doublet d6  6 deuterium DCC  Dicyclohexylcarbodiimide DCM  Dichloromethane DCU  Dicyclohexylurea dd  doublet of doublets ddd  doublet of doublets of doublets DMAP  N,N’-dimethylaminopyridine DMF   N,N’-dimethylformamide DMSO  Dimethylsulfoxide DSC  Differential scanning calorimetry xvi  dt  Doublet of triplets e-  Electron E1/2  Half-wave potential  Et  Ethyl g  grams GPC  Gel permeation chromatography hν  indicates light; h is Planks constant, and ν is the photon frequency HMBC Heteronuclear correlation spectroscopy HPLC  High performance liquid chromatography IR  Infrared spectroscopy J  J value kcal  kilocalorie λ  wavelength M  Molar  m  multiplet  Mn¯¯¯   number-average molecular weight  Mw¯¯¯   weight-average molecular weight  MeOH  Methanol MHz  Megahertz min.  minute mL  Millilitre mM  Millimolar    mmol  Millimoles xvii  mol  Moles MS  Mass spectrometry nm  Nanometer NFO  Non–first order triplet NMP  N-methyl-2-pyrrolidone NMR  Nuclear magnetic resonance  Nu  Nucleophile ORTEP Oak Ridge thermal ellipsoid plot p  Para PDI  Polydispersity index ppm  parts per million q  Quartet ROMP  Ring opening metathesis polymerization s  Singlet t  Triplet Tg  Glass transition temperature TGA  Thermogravimetric analysis THF  Tetrahydrofuran TM  Trademark tt  Triplet of triplets UV  Ultraviolet UV-vis Ultraviolet visible V  Volts xviii  Acknowledgements  I owe my deepest gratitude to my supervisor Dr. Alaa Abd-El-Aziz, for all of his inspiration, guidance and support, without whom this research would not have been possible.  I would also like to thank the members of my committee Dr. Kevin Smith and Dr. Stephen McNeil for their excellent advice regarding the writing of this thesis.  A huge thank you to Dr. Paul Shipley for always making time for my incessant questions regarding NMR interpretation and theory.   To the members of the lab both past and present, thank you for sharing your expertise and the fun times.  Thank you, Chris Rock for your efforts in the Methacrylate project.  In particular, I would like to thank my fiancé Patrick Oliver Shipman for all of his help completing this enormous task as well as for his excellent culinary skills.   I would also like to thank my family and friends, especially Lottie Joyce, Alexander Winram, Cynthia Winram, Christine McIntyre and Kelly Brodofske, for all of their encouragement.  Patrick, I am not only grateful of your cooking skills but also for your patience and understanding during the whole thesis writing process.   1  Chapter 1:  Introduction 1.1 The chemistry of ferrocene In 1951, Peter Pauson and Tom Kealy reported the first synthesis of ferrocene.1, 2  These two chemists were attempting to prepare fulvalene when they inadvertently prepared ferrocene; however, they proposed the wrong structure for the compound (Figure 1.1 a).  Woodward and Wilkinson recognized that the proposed 10 e- structure was unlikely and proposed the 18 e- bis(η5-cyclopentadienyl)iron(II) structure which was confirmed through x-ray crystallography in 1952 (Figure 1.1 b).  Ferrocene was determined to consist of two cyclopentadiene rings located in planes above and below an iron atom.2, 3  Organometallic molecules that have this sort of “sandwich structure” are referred to as metallocenes.  Figure 1.1: Proposed structures for ferrocene. One of the more interesting features of ferrocene is that the cyclopentadiene rings can undergo chemical reactions similar to that of organic aromatic compounds.  For example, Friedel-Crafts acylation of the cyclopentadiene rings proceeds in the presence of a Lewis acid.4, 5  The chemistry of ferrocene is quite diverse and many derivatives can be prepared. This is illustrated in Figure 1.2 which shows a sample of the different ferrocene derivatives that can be 2  synthesized. BuLi Figure 1.2: The reactivity of ferrocene. 6, 7 Four oxidation states have been demonstrated for ferrocene, the 18 e- ferrocene is an electron rich species that can be oxidized to form its 17 e- ferrocinium ion by either chemical or electro-oxidation (Figure 1.3).6  Using cyclic voltammetry more extreme oxidation states have been demonstrated by the groups of Laviron (reduction to 19 e-, DMF) and Bard (oxidation to 16 e-, SO2). Studies of the 18 e- ferrocene to the 17 e- ferrocinium ion cyclic voltammetry wave 3  shows that the oxidation of ferrocene is not only reversible but highly reproducible.8, 9  The reproducibility of this reaction is such that ferrocene is often used as an internal reference for cyclic voltammetric studies.  Investigations into the electrochemical behaviour of a number of substituted ferrocenes has revealed that electron donating substituents lead to lower redox potentials while electron withdrawing substituents lead to increased redox potentials.10   Figure 1.3: Potentials for the oxidation states of ferrocene as determined by cyclic voltammetry. (Potentials are given versus a saturated calomel reference electrode.)6   The development of ferrocene derivatives with reactive functional groups has led to the incorporation of these complexes into large molecules and polymers.2, 3, 11  Arimoto and Haven were the first to produce polymers containing ferrocene with the polymerization of vinyl ferrocene.11  Since then numerous polymers with ferrocene in the side chain or backbone have been prepared.12-14  The continued interest in the incorporation of ferrocene into polymers stems from its high stability towards heat, UV radiation and γ-radiation as well as the electrochemical behaviour.1, 11, 13, 15 Ferrocene compounds are some of the most studied organometallic compounds in chemistry.  Their diamagnetic nature allows for thorough characterization through nuclear magnetic spectroscopy (NMR).  In a 1H NMR spectrum, ferrocene shows up as a singlet at 4.2 ppm while in a 13C NMR spectrum it shows up as a singlet at 68 ppm (in CDCl3).  The shielding 4  and deshielding effects of substituents on cyclopentadienyl rings of ferrocene, mirror the trends found for aromatic organic compounds.   1.2 The synthesis and chemistry of η6-(arene)-η5-cyclopentadienyliron(II) hexafluorophosphate complexes  Ferrocene is capable of exchanging one of its cyclopentadiene rings with an arene; this type of ligand exchange was first reported in 1963 by Nesmeyanov, Vol’kenau and Bolesova.16  They reacted ferrocene with arene ligands using aluminum chloride in the presence of powdered aluminum at temperatures between 80-165 oC (Figure 1.4).  The aluminum was used to prevent the oxidation of ferrocene to the ferricinium-cation.  The reaction gave 30-66% yield of the η6-(arene)-η5-cyclopentadienyliron(II) which can be isolated as the tetrafluoroborate or hexafluorophosphate salt.  While many examples of this reaction use decalin as a solvent, an additional solvent is not necessary for arenes which are liquid at reaction temperature.  Figure 1.4: General synthesis for η6-(arene)-η5-cyclopentadienyliron(II) hexafluorophosphate complexes. η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate salts can be synthesized by reacting ferrocene with the appropriate halo-benzene compounds using the general conditions described above. These η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate salts are able to undergo many reactions utilizing the haloarene ring (Figure 1.5).6  One of the most useful 5  properties of η6-(haloarene)-η5-cyclopentadienyliron(II) compounds is that they can undergo metal mediated nucleophilic aromatic substitution reactions under mild reaction conditions (Figure 1.6).6, 17, 18  The susceptibility of the complexed arene to nucleophilic aromatic substitution is due to the strong electron withdrawing capabilities of the cyclopentadienyliron.  In substitution reactions, the nucleophile (amine, alcohol or thiol) attacks the ipso carbon halo-arene ligand forming a cyclohexadienyl intermediate which is very acidic (Figure 1.6).  Dehydrohalogenation of the cyclohexadienyl intermediate is easily accomplished using a weak base such as K2CO3.  Figure 1.5: Reactivity of η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate salts. 6   6   Figure 1.6: Nucleophilic aromatic substitution of a η6-(haloarene)-η5-cyclopentadienyliron(II) (hexafluorophosphate counter ion omitted for clarity). 6    Cyclic voltammetric studies of η6-(arene)-η5-cyclopentadienyliron(II) hexafluorophosphate complexes have revealed up to 4 possible oxidation states (Figure 1.7).6  For complexes where the arene is hexamethylbenzene the cyclic voltammetry waves of the four oxidation states are electrochemically and chemically reversible, and the 17 e-, 18 e- and 19 e- states have all been isolated in their crystalline form.  For other η6-(arene)-η5-cyclopentadienyliron(II) hexafluorophosphate salts the first reduction to the 19 e- species is typically reversible, while the second reduction is reversible only when a suitable arene ring is chosen. This is due to the relative instability of the 20 e- species.19  Figure 1.7: Potentials for the oxidation states of η6-(hexamethylbenzene)-η5-cyclopentadienyliron(II) as determined by cyclic voltammetry. (Potentials are given versus a saturated calomel reference electrode.)6   7   The mild reaction conditions permitted by the use of η6-(haloarene)-η5-cyclopentadienyliron(II) to form aryl ethers, allows for the synthesis of molecules that would otherwise (without the iron) be difficult to obtain.17, 18, 20, 21  Decomplexation of the cationic cyclopentadienyliron moiety to give the organic arene is easily performed, making the η6-(arene)-η5-cyclopentadienyliron(II) moiety a useful tool for organic synthesis.  There are three strategies for the removal of the cyclopentadienyliron(II) moiety from various η6-(arene)-η5-cyclopentadienyliron(II) complexes; pyrolysis, electrolysis and photolysis.21  Pyrolysis is the most harsh method for the removal of the cyclopentadienyliron(II) moiety, requiring temperatures above 200oC.  This strategy is not commonly used as it requires thermally stable arenes and often yields less of the arene compared to the other two methods. Advantages of pyrolysis include short reaction times and compounds do not need to be soluble.  Electrolysis is less harsh then pyrolysis requiring potentials of -1.5 to -2.5 V.  While this method is quite effective, the presence of reducible substituents on the arene can lead to side reactions.  Photolysis is often the best strategy for the removal of the cyclopentadienyliron(II) moiety; as it can be used with arenes that are heat sensitive as well as arenes with reducible substituents.  The photolytic cleavage of the cyclopentadienyliron moiety was thoroughly studied by Schuster et al who proposed that irradiation caused ring slippage from η6 to η4.22  The iron could then be nucleophilically attacked by the solvent acetonitrile, displacing the arene ligand. At -40 oC the product of this reaction is the tris(acetonitrile)cyclopentadienyl iron species seen in Figure 1.8; however, at 20 oC the reaction continues to give the organic product, iron salts and ferrocene.23, 24 8   Figure 1.8: Proposed sequence for the photolysis of  η6-(arene)-η5-cyclopentadienyliron(II) complexes.22  X- is a counter ion such as PF6-.  Characterization of η6-(arene)-η5-cyclopentadienyliron(II) complexes can be performed using several different methods including IR, MS, UV-vis spectrophotometry, X-ray crystallography and NMR spectroscopy.21  Unfortunately, these species often have a low volatility making MS difficult and it is very difficult to grow crystals of these structures that are of adequate quality for crystallography.  While many transition metal complexes are paramagnetic, η6-(arene)-η5-cyclopentadienyliron(II) complexes are diamagnetic allowing for their characterization through NMR.  Compared to ferrocene which appears at approximately 4.2 ppm, the cyclopentadiene ring of η6-(arene)-η5-cyclopentadienyliron(II) complexes shows a significant downfield shift appearing at approximately 4.9-5.6 ppm in 1H NMR spectra. This shift is possibly due to the delocalization of the positive charge throughout the cyclopentadiene ring.25  The complexed arene appears at approximately 6.0 -7.0 ppm, which is upfield compared 9  to free arenes, this is due to increased shielding resulting from metal to ligand π backbonding.  In 13C NMR spectra the complexed arenes appear at 70-95 ppm for CAr-H and 100-135 ppm for quaternary carbons, which is farther upfield then non-complexed arenes.  1.3 Synthesis and chemistry of µ-alkyne-bis(tricarbonylcobalt) complexes  The replacement of the bridging carbonyl groups of dicobalt octacarbonyl (Co2(CO)8) has been known since the mid 1950’s (Figure 1.9).26  This complex can form an intermediate in cyclicization reactions such as the Pauson-Khand reaction.  The alkyne-(Co2(CO)6) complex can also stabilize a carbonium ion center and allow for regio-specific nucleophilic coupling reactions.27  The cobalt carbonyl can also act as a protecting group for triple bonds and can be removed using oxidative cleavage with ceric(IV) ammonium nitrate ((NH4)2Ce(NO3)6) in acetone.28  Figure 1.9: General synthesis of alkyne-cobalt carbonyl complexes.  Purification of µ-alkyne-bis(tricarbonylcobalt) complexes usually involves chromatography on alumina or silica.29  The incorporation of the cobalt carbonyl is usually confirmed with IR spectroscopy, where the disappearance of the C≡C stretching vibration (weak band 2260-2100 cm-1) and the appearance of three sharp bands between 2100-2000 cm-1 indicate coordination of the cobalt to the alkyne.26, 30  The absence of a bridging carbonyl band at 1859 cm-1 can be used to indicate that no excess cobalt carbonyl is present in a sample. 10   Cyclic voltammetric studies of PhC2Co2(CO)6 were done by Arewgoda et al. using Ag/AgCl electrode in acetone at  -30 oC found two one electron waves at -0.82 V and -1.56 V.{{377 Arewgoda, M. 1982}} However, at higher temperatures the anodic peak current decreased indicating decomposition of the radical anion. Complex (t-Bu)2C2Co2(CO)6 under the same conditions also found two one electron waves at -1.03 V and -1.8 V as well as, a smaller wave at -1.9 V.    1.4 Metal containing polymers  Metal containing polymeric materials are a desired synthetic goal due to their potential use as electronic or magnetic materials or as precursors for ceramics and metallic nanoparticles.31  Iron and cobalt containing polymers are important classes of metal containing materials due to their possible magnetic and redox properties.31  Cobalt nanomaterials are often prepared by the thermolysis of Co2(CO)8 in the presence of phosphines or carboxylic acids, which prevent aggregation into larger agglomerates; however, this stabilization can also be achieved by directly incorporating the organometallic components into polymers. Shi and coworkers have recently reported on the pyrolytic ceramization of hyperbranched poly(ferrocenylphenylenes) containing cobalt carbonyl to produce soft ferromagnetic ceramics with high magnetizability.32   While ferrocene and η6-(arene)-η5-cyclopentadienyliron(II) are usually incorporated into monomers which are then polymerized, there are two possible strategies for the inclusion of cobalt into polymers.  The most common strategy is coordination of the cobalt carbonyl post polymerization; however, the cobalt can also be added prior to polymerization.   11  1.5 Scope of the present work  This thesis focuses on the incorporation of transition metals into the backbone or side chains of various classes of polymers and oligomers.  Small changes to a monomer, such as change of functional group or incorporation of dyes or metals can result in large property changes in the resulting polymers.  This well known adage is a driving force for the production of new polymeric materials where the incorporation of functional groups or other structural moieties provides materials with useful properties. Chapters two and three focus on the synthesis of norbornene and methacrylic ester polymers and oligomers with iron and cobalt in the side chain.  To this end three different polymers will be discussed in each chapter, polymers containing a ferrocene moiety as well as an µ-alkyne-bis(tricarbonylcobalt) moiety.  The next two polymers incorporate one or two η6-(arene)-η5-cyclopentadienyliron(II) hexafluorophosphate moieties as well as an µ-alkyne-bis(tricarbonylcobalt) moiety. Chapter four presents the synthesis of two different types of condensation polymers synthesized utilizing the nucleophilic aromatic substation reaction.  The first type has η6-(arene)-η5-cyclopentadienyliron(II) hexafluorophosphate moieties as well as a alkyne group, while the second type has the alkyne group complexed to cobalt carbonyl. Chapter 5 details the synthesis of silyloxane polymers that incorporate η6-(arene)-η5-cyclopentadienyliron(II) hexafluorophosphate moieties.  This project lays the foundation for future work within the Abd-El-Aziz group with polysiloxanes and the incorporation of transition metals. 12  1.6 Materials and instrumentation All reagents were purchased from Sigma-Aldrich and used without further purification. All general solvents were HPLC grade and used without further purification. The dry dichloromethane and the dry THF, used in water and oxygen sensitive reactions, were HPLC grade solvents that were dried and degassed using established procedures.33   1H and 13C NMR spectra were recorded at 400 MHz and 100 MHz respectively on a Varian Mercury Plus spectrometer equipped with a gradient field probe. The chemical shifts were referenced to residual solvent peaks and coupling constants reported in Hz. Infrared (IR) spectroscopy was recorded on a Nicolet IR200 FT-IR by making thin layer films of each compound on NaCl plates or by making KBr pellets.  Thermogravimetric analysis (TGA) was performed on a Mettler–Toledo TGA/SDTA851e with a heating rate of 20 oC/min under a steady stream of nitrogen (50 mL/min). Differential scanning calorimetry (DSC) was performed on a Mettler DSC821e with a heating rate of 20oC/min under a 50mL/min flow of nitrogen.  Cyclic voltammetric experiments were performed using a conventional three-electrode cell. In these studies the working electrode was a glassy carbon disk electrode (ca. 2 mm diameter), the auxiliary electrode was a Pt wire, and a (Ag/AgCl) reference electrode was utilized. Temperatures at -40 °C were obtained using an acetone/dry ice mixture. The concentration of the analyte was 2.0 mM in propylene carbonate, while that of the supporting electrolyte, Tetrabutylammonium perchlorate, was 0.1 M. The solutions were deoxygenated with nitrogen prior to use and an EG&G Princeton Applied Research model 263 A potentiostat was used in all experiments with a scanning rate of 0.2 V/s. 13  GPC was performed on a Polymer Labs PL-GPC 50 plus with a PL-AS RT auto-sampler and PL-RI detector. The eluent was THF flowing at 1 mL/min at 30 °C. Two PLgel mixC columns were setup in series. The molecular weights were calculated against PS-H polystyrene standards. All crystallographic materials and instrumentation are described in the appendices (p. 171).  14  Chapter 2:   glyph1197orbornene based polymers 2.1 Introduction Norbornene is a highly strained bicyclic olefin that is often used for the synthesis of polymeric materials.  Norbornene, which is also known as bicyclo[2.2.1]hept-2-ene, can be polymerized in four ways: radical polymerization, cationic polymerization, ring opening metathesis polymerization (ROMP) or vinyl polymerization (Figure 2.1).34  Each type of polymerization provides products with different structures and properties. However, this thesis focuses on ROMP  as it is known to give a more uniform polymer.  Figure 2.1: Four strategies for norbornene polymerization. Ring opening metathesis polymerization is a process by which highly strained cyclic olefins are opened to form polymeric materials.  Catalysts containing transition metals such as ruthenium, molybdenum and tungsten are known to be quite useful for this process.35  ROMP is an olefin metathesis reaction where a transition metal alkylidene complex reacts with the 15  norbornene alkene in a [2+2] fashion to give a metalacyclobutane ring as an unstable intermediate (Figure 2.2).  A cycloreversion reaction of the metalocyclobutane ring leaves a cyclopentane ring with a metal alkylidene. This complex can then react repeatedly with norbornene to form a growing chain.  Many of the catalysts used for ROMP can also catalyze ring closing metathesis; this means that eventually a reaction equilibrium may be reached where both processes are occurring simultaneously.  It is often beneficial to terminate the polymerization before this equilibrium is established so that the polymers are more uniform in size (have a lower polydispersity index, PDI).  ROMP can be terminated by adding ethyl vinyl ether, which reacts with the metal to cleave off the polymer chain forming a M=CHOEt carbene complex. This complex is unreactive toward further metathesis reactions.  Figure 2.2: Ring opening metathesis of norbornene.  Ruthenium catalysts such as those developed by Grubbs are very useful for the ROMP of norbornene derivatives due to their high level of tolerance for various functional groups and pendent moieties.36  ROMP with the Grubbs catalysts has been demonstrated for norbornenes with pendent carboxylic acid,37 amino acid,38 ether, ester,39, 40 decaboranes,41 and siloxanes.42  Previous work done by Abd-El-Aziz et al. has shown that the first generation of Grubbs catalyst can be used to prepare polynorbornenes with η6-aryl-η5-cyclopentadienyliron(II) hexafluorophosphate groups in their side chain (Figure 2.3).39, 40  Polynorbornenes that contained azo dyes and η6-aryl-η5-cyclopentadienyliron(II) hexafluorophosphate groups in their side chain, were also prepared.  The present work builds on previous research by showing that alkyne 16  coordinated dicobalt hexacarbonyl can also be incorporated into polymers (pre-polymerization).  In this chapter, three different classes of highly metallated polynorbornenes were synthesized, one with neutral ferrocene and cobalt carbonyl-alkyne moieties and two that contained cationic η6-arene-η5-cyclopentadienyliron(II) and cobalt carbonyl-alkyne moieties.  All of the polymerizations utilized Grubbs 2nd generation catalyst.  Figure 2.3: A few examples of polynorbornenes with η6-aryl-η5-cyclopentadienyliron(II) hexafluorophosphate groups in their side chain. 17  2.2 Synthesis and characterization of polynorbornenes containing organoiron and cobalt carbonyl 2.2.1 Synthesis of a norbornene monomer containing ferrocene  The first step in the 5 step synthesis of the ferrocene-containing norbornene monomer was to prepare mono-acetyl ferrocene (2.3) through the acetylation of ferrocene (2.1) (Scheme 2.1).  This was accomplished using acetic anhydride (2.2) in concentrated phosphoric acid according to standard methods.7  Treatment of the mono-acetyl ferrocene with iodine and pyridine followed with the addition of 0.6 M NaOH afforded carboxylic acid ferrocene (2.4) (Scheme 2.1).4  Fe2.1OOO2.2H3PO4K2CO3Fe2.3OI2, pyridine0.6 M NaOHFe2.4OHO Scheme 2.1: Synthesis of complex 2.4.  Steglich esterification between mono-carboxylic acid ferrocene and 2-butyne-1,4-diol (2.5) was accomplished using DCC and DMAP in a DCM/DMF solvent mixture (Scheme 2.2).  Attempts to perform this reaction in DCM alone gave a mixture of starting material and product due to the poor solubility of the 2-butyne-1,4-diol. Purification of the crude product on silica using ether and hexanes for the mobile phase gave the product in the second fraction, which was isolated as an orange-red solid. 18  Fe2.4OHOHO OHDCCDMAPDCM/DMF2.5Fe2.6OOOH+ Scheme 2.2: Synthesis of complex 2.6.  The 1H NMR spectrum for compound 2.6 can be seen in Figure 2.4. The substituted cyclopentadiene ring gives two NFO triplets at 4.79 and 4.48 ppm.  Between 4.20 and 4.29 ppm there are two overlapping peaks, one resonance is a singlet which is due to the non-substituted cyclopentadiene while the other is a triplet due to the methylene next to the alcohol.  The methylene of the ester appears at 4.86 ppm.  It is interesting to note that the methylenes of the butyne-diol moiety appear as triplets due to long range coupling to each other through the triple bond (J=1.8 Hz). 19   Figure 2.4: 1H NMR spectrum of compound 2.6 acetone-d6. The 13C NMR spectrum of complex 2.6 in chloroform shows the three expected resonances for the mono-substituted ferrocene at 71.9, 70.5 and 70.1 ppm (Figure 2.5).  The quaternary carbon of the substituted ferrocene cannot be clearly seen as it overlaps with one of the other resonances.  The carbonyl carbon is visible at 171.4 ppm, while the alkyne carbons appear at 84.8 and 81.0 ppm.  Finally the methylenes appear at 52.1 and 51.4 ppm.   20   Figure 2.5: APT 13C NMR spectrum of compound 2.6 in CDCl3.  Crystals of complex 2.6, suitable for X-ray crystallography, were grown from an ether/hexanes solvent mixture(60/30); the ORTEP diagram for this complex can be seen in Figure 2.6.  Lists of structural factors and other crystallographic data can be found in the appendix on page 171.  The cyclopentadiene rings are coplanar and eclipsed as was previously seen for complex 2.4.43   21   Figure 2.6: ORTEP diagram of complex 2.6. The next step in the preparation of of the target monomer was to incorporate norbornene.  A mixture of endo and exo 5-norbornene-2-carboxylic acid (2.7) was reacted with complex 2.6 via the Steglich esterification reaction giving the norbornene monomer 2.8 (Scheme 2.3).  As the analysis of complex 2.8 is quite complicated it was also necessary to synthesize a single isomer, 2.8 exo, in order to fully elucidate the spectral analysis.  Complex 2.8 exo was synthesized using the exo-5-norbornene-2-carboxylic (2.7 exo) acid that was prepared according to standard techniques.  Both complex 2.8 and complex 2.8 exo were isolated as dark orange solids. 22   Scheme 2.3: Synthesis of complex 2.8.  The 1H NMR of complex 2.8 clearly shows the incorporation of the norbornene (Figure 2.7).  The olefinic hydrogens of the norbornene appeared between 5.90 and 6.20 ppm, while the aliphatic resonances (complicated by the mixture of endo and exo norbornene) were seen between 3 and 1 ppm.  An expanded view of the norbornene olefinic hydrogen resonances can be seen in Figure 2.7. Integration of the endo and exo peaks that appear 5.93 and 6.10 ppm, respectively, clearly indicate that the compound mixture is 78 % endo and 22 % exo. Due to the complexity of the NMR spectra of the endo and exo mixture of complex 2.8 a pure sample of complex 2.8 exo was synthesized to help elucidate the spectra. It is beneficial to compare the spectrum for the endo/exo mixture of complex 2.8 with its single exo isomer (2.8 exo) and the staring material (2.6) (Figure 2.8).  For the complex 2.8 exo the formation of the ester can be confirmed by the downfield shift of one of the methylenes from beneath the non-substituted cyclopentadiene peak at ~4.25 ppm (complex 2.6) to beneath one of the substituted cyclopentadiene peaks at ~4.8 ppm.  The overlapping of the methylene peak and one of the substituted cyclopentadiene peaks is confirmed through the integration of 4 for that peak.  For the endo portion of complex 2.8 the methylene protons appear as two doublets of triplets between 4.91-4.87 ppm.   23   Figure 2.7: 1H NMR spectrum of complex 2.8 in acetone-d6. OOOFeO24   Figure 2.8: 1H NMR spectral comparison of complexes 2.6, 2.8 exo and 2.8 in acetone-d6.  The 13C NMR spectrum for complex 2.8 in acetone, like the 1H NMR spectrum indicates a mixture of both endo and exo structures (Figure 2.9).  The carbon atoms that are more distant from the norbornene start to overlap, in fact the methylene furthest from the norbornene has only one resonance for both the endo and the exo isomers.  The ferrocene carbons and adjacent carbonyl carbon are also distant enough from the norbornene that the endo and exo resonances appeared as a single peak.  The resonances for the endo and exo norbornene olefin carbons appeared as four peaks between 134 and 140 ppm, while the other ten norbornene resonances appeared between 29 and 51 ppm (one overlapped with the solvent peak).  The four alkyne resonances appeared between 80 and 85 ppm, while the three resonances for the adjacent methylenes were found between 51 and 53 ppm.  The quaternary carbon of the ferrocene was 25  found at 71.0 ppm.  However, only two of the expected carbonyl carbons are apparent, 173.88 and 170.93. A quick analysis of the HMBC NMR spectrum (Figure 2.10) reveals that the resonance at 173.88 show secondary coupling to the methylene of the endo complex at 4.72 ppm and to a norbornene peak at 1.36 ppm, indicating that it belongs to the norbornene ester carbonyl. The exo norbornene ester carbonyl at 175.61 ppm is only evident in the HMBC NMR spectrum, where coupling to the methylene at 4.79 ppm and to the norbornene peak at 1.36 ppm is apparent. It is useful at this point to examine a small portion of the HSQC NMR spectrum for complex 2.8 as it confirms the overlapping of the methylene protons and cyclopentadiene protons at 4.88 ppm (Figure 2.11).  Figure 2.9: APT 13C NMR spectrum of complex 2.8 in acetone-d6.   OOOFeO26   Figure 2.10: HMBC NMR spectrum of complex 2.8 in acetone-d6. 27   Figure 2.11: HSQC NMR spectrum of complex 2.8 in acetone-d6. Arrow indicates the overlapping methylene resonance.  2.2.2 Polymerization of a norbornene monomer containing ferrocene  Polymerization of complex 2.8 was done using Grubbs 2nd generation catalyst in DCM.  While this catalyst is known to react both with alkene and alkyne functional groups, we were curious to see how it performed with a monomer that contained both an alkyne group and norbornene.44, 45 This polymerization produced what appeared to be a cross linked polymer (Scheme 2.4).  This material was observed to swell without dissolving in organic solvents such as acetone, DCM, chloroform, DMSO, THF and DMF as is typical of cross-linked materials.46  28   Scheme 2.4: Synthesis of complex 2.9.  2.2.3 Synthesis of a norbornene monomer containing both ferrocene and cobalt Since the attempts to polymerize complex 2.8 directly resulted in a cross linked material (2.9), it was necessary to coordinate the cobalt carbonyl to the alkyne moiety of complex 2.8 prior to polymerization (Scheme 2.5).  During the synthesis of 2.11, the bridging carbonyl groups of the two cobalt atoms were exchanged for the alkyne resulting in the evolution of carbon monoxide.  Once the reaction reached completion, the excess cobalt carbonyl needed to be removed from the reaction. This is especially important as the degradative products of Co2(CO)8 are paramagnetic and greatly affect the NMR spectral analysis.  When complex 2.11 was dissolved in acetone and left open to the atmosphere, a precipitate formed in the solution.  This precipitate was easily removed by filtration through celite.  After the precipitate was removed the product was isolated by removal of the solvent in vacuo.   29   Scheme 2.5: Synthesis of complex 2.11. The 1H NMR spectrum of 2.11 showed a noticeable shift of the methylene resonances nearest the triple bond from ~4.9 and ~4.7 ppm to ~5.4 ppm due to electron deshielding caused by the coordination of the cobalt carbonyl to the alkyne (Figure 2.12).  The methylene region that appears from 5.25 -5.53 ppm is fairly complicated due to the two isomers of the complex. In order to fully understand why there are 10 peaks in this region it was necessary to synthesize the exo isomer of complex 2.11 (2.11 exo).  A comparison of 2.11 and 2.11 exo (Figure 2.13) allowed for the full analysis of this region.  The 1H NMR spectrum for  2.11 exo shows that one of the methylenes (presumably the one closest to the norbornene) is affected by the chiral nature of the norbornene, causing the two protons to appear as 2 doublets at 5.49 and 4.43 ppm.  The other methylene is not as affected by the proximity to the norbornene causing it to appear as a singlet at 5.50 ppm overlapping with one of the doublets.  This same pattern of multiplicity is also seen for the endo form of complex 2.11 in the isomeric mixture (endo peaks indicated by 30  arrows).   Figure 2.12: 1H NMR spectrum of complex 2.11 in acetone-d6.  O OOOFeCoCoCOCOOCOC COOC31   5.265.325.385.445.50 ppm122.112.11 exo Figure 2.13: Expansion of the 1H NMR resonances in acetone-d6 of the methylenes next to the coordinated cobalt moieties of 2.11(exo/endo mixture) and 2.11 exo.  *Arrows indicate endo resonances. Deshielding of the methylene groups adjacent to the alkyne cobalt complex is apparent in the 13C NMR spectrum of the complex 2.11, where the four representative peaks shift from 52.63, 52.25, 52.02 and 50.12 ppm (complex 2.8) to 65.79, 65.76, 65.56 and 65.45 ppm (complex 2.11, Figure 2.14).  This is confirmed in the HSQC NMR spectrum of complex 2.11 (Figure 2.15).  It can be seen that the proton resonances due to the methylenes at 5.53-5.25 ppm are directly connected to the carbon resonances between 65.4 and 65.8 ppm.  The carbon 32  resonances of the alkyne and carbonyl carbons coordinated to the cobalt are not readily apparent in the 13C NMR spectrum due to broadening caused by the presence of the cobalt.  However, the alkyne carbon resonances can be visualized in the HMBC NMR spectrum for complex 2.11 as the peaks at 5.46 and 90.84 ppm (Figure 2.16).     Figure 2.14: APT 13C NMR spectrum of complex 2.11 in acetone-d6. O OOOFeCoCoCOCOOCOC COOC33   Figure 2.15: HSQC NMR spectrum of complex 2.11 in acetone-d6. 34   Figure 2.16: HMBC NMR spectrum of complex 2.11 in acetone-d6.  The carbonyl carbons coordinated to the cobalt cannot be seen in the various NMR spectra shown (Figure 2.14-Figure 2.16).  However, IR spectroscopy can be used to indicate their presence.  The IR spectrum for complex 2.11 shows three distinct bands in the 2100 cm-1 region of the IR spectrum which is a typical band pattern for the carbonyl stretches of an alkyne cobalt carbonyl structure (Figure 2.17).26, 47 35   Figure 2.17: IR spectral comparison of complexes 2.8 and 2.11.  2.2.4 Polymerization of a norbornene monomer containing both ferrocene and cobalt Polymerization of the multiple metal containing complex 2.11 was achieved using Grubbs 2nd generation catalyst in DCM (Scheme 2.6).  The success of the polymerization is supported by the 1H NMR with an upfield shift of the norbornene olefinic protons from a multiplet at 5.90-6.25 ppm to a broad peak at 5.00-5.55 ppm overlapping with the methylene resonances.  There is also broadening of many of the resonances as is typical for the 1H NMR spectra of polymers (Figure 2.18).  The polymers were not soluble enough to acquire a 13C NMR spectrum. The molecular weights of this polymer will be discussed later in section 2.4. 36   Scheme 2.6: Synthesis of polymer 2.12.   Figure 2.18: 1H NMR spectrum of polymer 2.12 in CDCl3. OOOOFeCoCoCOCOOCOCCOOCn37  2.3 Synthesis and characterization of η6-arene-η5-cyclopentadienyliron(II) and cobalt containing polynorbornenes 2.3.1 Synthesis of a norbornene monomer containing alkyne-hexacarbonyl cobalt and two η6-chloroarene-η5-cyclopentadienyliron(II) moieties In the previous section, ferrocene and cobalt carbonyl were incorporated into norbornene which was then polymerized.  This section of chapter 2 details the synthesis of norbornene monomers which contain  η6-arene-η5-cyclopentadienyliron(II) moieties as well as an alkyne-hexacarbonylcobalt moiety.  Using a similar procedure as developed by Nesmeyanov et al.  complexes 2.14 a-c were prepared (Scheme 2.7).16  Compounds that contain these η6-chloroarene-η5-cyclopentadienyliron(II) hexafluorophosphate salts can decompose when exposed to light, so complexes 2.14 a-c and all subsequent derivatives were stored and reacted in the dark. FeClR2.12.13 a-cAlCl3, AlFe+PF6-2.14 a-ca  R = Clb  R = Hc  R = CH3ClR Scheme 2.7: Synthesis of complexes 2.14 a-c.  Norbornene monomers containing two η6-chloroarene-η5-cyclopentadienyliron(II) hexafluorophosphate moieties and dicobalt hexacarbonyl were prepared, to determine if increasing the amount of cationic iron in the polymers would have any effect on their synthesis or thermal properties. As shown previously, η6-chloroarene-η5-cyclopentadienyliron(II) hexafluorophosphate salts are known to undergo nucleophilic aromatic substitution.  Complex 38  2.14 a possesses two positions where substitution can occur and is highly reactive towards alcohol, amine and thiol nucleophiles.  The incorporation of two η6-chloroarene-η5-cyclopentadienyliron(II) hexafluorophosphate moieties was accomplished by first finding a compound that had three reactive sites.  4,4-bis(4-hydroxyphenyl)valeric acid (2.15) is ideal for the incorporation of two iron centers due to its two phenolic alcohols which were reacted with complex 2.14 a leaving the carboxylic acid free for further reactions (Scheme 2.8).  Previous reports on the synthesis of complex 2.16 used a THF/DMF solvent mixture at 50 oC; however, using DMF alone at room temperature works as well.48  The DMF is easily removed when the product is precipitated into 1.2 M HCl and washed with water.  Scheme 2.8: Synthesis of complex 2.16. 39    Complex 2.17 was synthesized using the Steglich esterification between the valeric acid complex 2.16 and 2-butyne-1,4-diol (2.5) (Scheme 2.9).  Complex 2.17 has a free alcohol which can allow for its incorporation into various monomers.  Scheme 2.9: Synthesis of complex 2.17.  The 1H NMR of complex 2.17 shows all of the expected resonances (Figure 2.19).  The non-complexed arene resonances appear at 7.48 and 7.34 ppm, while the complexed arene resonances are found at 6.82 and 6.52 ppm.  The cyclopentadiene resonance appears at 5.38 ppm 40  and the two methylenes adjacent to the triple bonded carbons are at 4.71 and 4.23 ppm.  The other two methylenes appear as triplets at 2.56 and 2.24 ppm and finally the methyl group appears at 1.76 ppm.  Figure 2.19: 1H NMR spectrum of complex 2.17 in acetone-d6. * denotes H2O. The 13C NMR spectrum for complex 2.17 (Figure 2.20) contains all 18 of the expected peaks plus acetone at 30.6 and 206.9 ppm.49  The carbonyl carbon resonated at 172.9 ppm.  While the non-complexed arene resonances were observed at 151.7, 147.6, 130.4 and 121.1 ppm.  The complexed arenes were found at 133.6, 104.5, 87.5 and 76.7 ppm while the cyclopentadiene resonances appeared at 80.3 ppm.  The alkyne carbon resonances were found at 86.6 and 79.3 ppm while the adjacent methylene carbons resonated at 52.5 and 50.3 ppm.  The methylene carbon next to the carbonyl carbon of the organometallic moiety resonates at 30.2 ppm and is 41  actually found within the solvent residue peak.  The final methylene was found at 36.8 ppm, the quaternary carbon sandwiched between the arenes appeared at 46.0 ppm and the methyl resonated at 27.7 ppm.    Figure 2.20: APT 13C NMR spectrum of complex 2.17 in acetone-d6.  Steglich esterification esterification between complex 2.17 and 5-norbornene-2-carboxylic acid (2.7) produced complex 2.18.  The success of the reaction between complex 2.17 and the 5-norbornene-2-carboxylic acid (2.7) was determined through NMR spectroscopy.  The 1H NMR spectrum of complex 2.18 (Figure 2.21) shows both the appearance of the norbornene peaks at 6.19-5.87, 2.18-2.88, 1.95-1.85, and 1.48-1.26 ppm as well as the downfield shift of the methylene protons adjacent to the newly formed ester to 4.76-4.64 ppm.  Unfortunately, the endo exo ratio of the sample could not be determined due to overlapping of the olefin peaks.   42   Scheme 2.10: Synthesis of complex 2.18.  43   Figure 2.21: 1H NMR spectrum of complex 2.18 in acetone-d6. The 13C NMR spectrum of 2.18 also shows the appearance of the norbornene olefin resonances at 138. 92, 138.52, 136.47 and 133.10 ppm (Figure 2.22).  Ten resonances can be seen for the other five carbons of the norbornene.  The formation of the ester is further confirmed by the upfield shift of the methylene carbons from 50.3 ppm to 52.56 and 52.59.  Of the forty five peaks in the 13C NMR spectrum thirty eight can be attributed to an endo/exo mixture of complex 2.18.  Upon a full analysis of the HSQC and HMBC NMR spectra for complex 2.18 it is possible to determine the identities of the exo and endo carbon resonances (Figure 2.23 and Figure 2.24).  The endo and exo resonances for each carbon get closer and closer together as the distance from the norbornene increases to the point where the methylene carbon between the alkyne and the valeric ester appears only as one peak at 52.16 ppm. The convergence of the endo and exo resonances at this point in the molecule was also seen for complexes 2.8.  The seven O OOOFe+ClFe+ClOO44  other peaks in the 13C NMR spectrum are of quite low intensity and can be attributed to a slight amount of starting material in the sample.  Figure 2.22: APT 13C NMR spectrum of complex 2.18 in acetone-d6. 45   Figure 2.23: HSQC NMR spectrum of complex 2.18 in acetone-d6. 46   Figure 2.24: HMBC NMR spectrum for complex 2.18 in acetone-d6.  Coordination of dicobalt octacarbonyl (2.10) to complex 2.18 gave the tetra metallic complex 2.19 (Scheme 2.11). The success of the reaction was determined through NMR and IR spectroscopies.  The IR showed the presence of the cobalt carbonyl bands situated around 2100 cm-1.  In the 1H NMR spectra of complex 2.19, the resonances of the methylenes adjacent to the alkyne have shifted downfield from 4.76-4.64 ppm (complex 2.18) to 5.48-5.17 ppm (complex 2.19) (Figure 2.25).  The splitting pattern of these resonances cannot be seen as they overlap with the cyclopentadiene peak.  The olefin resonances of the endo/exo mixture appear as discrete peaks in this spectrum, allowing for the ratio of isomers to be determined (63% endo and 37% exo).  The 13C NMR spectrum of complex 2.19 also shows a downfield shift from 52.59, 52.55 and 52.16 ppm (complex 2.18), to 65.60, 65.40 and 65.38 ppm (complex 2.19) for the methylene carbons adjacent to the alkyne (Figure 2.27).  Unfortunately, not all of the carbon resonances are 47  visible in the 13C NMR spectrum; the alkyne and carbonyl carbons coordinated to the cobalt cannot be seen due to broadening, also the two endo and exo carbonyl carbons of the norbornene are not visible.  Scheme 2.11: Synthesis of complex 2.19.  48    Figure 2.25: 1H NMR spectrum of complex 2.19 in acetone-d6.         49      Figure 2.26: APT 13C NMR spectrum of complex 2.19 in acetone-d6.  2.3.2 Polymerization of a norbornene monomer containing cobalt carbonyl and two η6-arene-η5-cyclopentadienyliron(II) moieties  Polymerization of complex 2.19 was done using Grubbs 2nd generation catalyst in a 50:1 ratio giving polymer 2.20 (Scheme 2.12). After 45 min. the polymers had mostly precipitated out 50  of solution and ethylvinylether was added to end cap any polymers still in solution.  The polymers were red in colour and displayed very different solubility than the monomer. The monomers had been soluble in DCM, acetone, DMSO, acetonitrile and DMF; however, the polymers showed no solubility in acetone or DCM, and were only partially soluble in acetonitrile, DMSO and DMF. 51   Scheme 2.12: Synthesis of polymer 2.20.  52   The 1H-NMR of polymer 2.20 shows the typical broadened peaks expected from a slightly soluble polymer (Figure 2.27). It is important to note that the olefinic hydrogens of the norbornene do not appear in the region as they did in the monomer (5.9-6.2 ppm).  These olefinic hydrogens have shifted upfield to reside as a part of the very broad resonance at 5.28 ppm, which also includes the cyclopentadiene and methylene resonances. There is a significant water peak in this spectrum that hides some of the polymer backbone peaks as well as some diethyl ether, which causes the aliphatic peak at 1.28 ppm to integrate for 3 extra protons.   The 13C-NMR analysis of polymer 2.20 could not be obtained because the polymer would not stay in solution long enough to obtain a good spectrum.  Figure 2.27: 1H NMR of polymer 2.20 in DMSO-d6.  53  2.3.3 Synthesis of a norbornene monomer containing a single η6-arene-η5-cyclopentadienyliron(II) moiety and cobalt carbonyl  In an effort to synthesize a monomer which contained a single η6-arene-η5-cyclopentadienyliron(II) hexafluorophosphate moiety, complex 2.14 a was reacted with 4-hydroxybenzoic acid (2.21).  Complex 2.22 was synthesized through modification to previously published procedures (Scheme 2.13).50  Previously, this reaction was done in a THF/DMF solvent mixture at an elevated temperature (60 oC) for 16 hours.  However this reaction works quite well at room temperature in pure DMF for 18 hours.  Keeping the temperature between 20-25 oC is very important to the success of the reaction because higher temperatures lead to partial disubstitution of the arene and decreased temperatures can lead to a mixture of starting material and product.  Scheme 2.13: Synthesis of complex 2.22.  As in the previous sections, the 2-butyne-1,4-diol (2.5) was reacted with complex 2.22 through a Steglich esterification reaction (Scheme 2.14).  By using a very large excess of the diol (2.5) it is possible to make complex 2.23 which has a terminal alcohol.  After purification, complex 2.23 was isolated as a yellow solid. 54   Scheme 2.14: Synthesis of complex 2.23.  The 1H NMR spectrum of complex 2.23 is consistent with the proposed structure (Figure 2.28).  The non-complexed arene resonances appear as doublets at 8.17 and 7.46 ppm, while the complexed arene resonances are at 6.84 and 6.61 ppm.  The cyclopentadiene resonance appears as a singlet at 5.39 ppm and the two methylene resonances are at 5.01 and 4.26 ppm.  The 1H NMR spectrum shows evidence of a second complex, with two very low intensity doublets at 7.7 and 7.4 ppm, as well as a second low intensity cyclopentadiene just slightly upfield of the complex 2.23 cyclopentadiene at 5.38 ppm. This slight impurity is most likely some residual starting material (2.22). 55   Figure 2.28: 1H NMR spectrum of complex 2.23 in acetone-d6.  The 13C NMR spectrum also confirms the expected structure (Figure 2.29). The carbonyl carbon resonance is visible at 165.51 ppm.  There are four resonances for the non complexed arene at 158.95, 133.52, 128.74 and 121.55 ppm.  The four resonances for the complexed arene, which are shielded by the iron, appear at 132.66, 105.83, 88.41 and 79.03 ppm.  The two resonances for the alkyne carbons appear at 87.55 and 79.43 ppm while the CH2 resonances can be seen at 53.89 and 50.81 ppm.  As in the 1H NMR spectrum, the 13C NMR spectrum also shows evidence of a second organoiron complex (2.22).  The low intensity residual starting material resonances appear at 131.19, 121.37, 88.30, 81.01 and 78.14. 56   Figure 2.29: APT 13C NMR spectrum of complex 2.23 in acetone-d6.  Attempts to further purify complex 2.23 were hampered by the presence of the η6-chloroarene-η5-cyclopentadienyliron(II) hexafluorophosphate moiety in both of the complexes.  Chromatography was unsuccessful as no solvent system could be found which would separate the complex from the impurity using either neutral alumina or silica as the solid phase. Indeed, both silica and alumina decomposed the sample.  The reaction between complex 2.23 and 5-norbornene-2-carboxylic acid (2.7) (Scheme 2.15) gave a yellow solid (complex 2.24) which showed the same solubilities as its precursor (2.23).  NMR and IR spectroscopies were used to determine if complex 2.24 was successfully synthesized. 57   Scheme 2.15: Synthesis of complex 2.24.  The 1H NMR spectrum for complex 2.24 can be viewed in Figure 2.30.  The 1H NMR shows the appearance of the endo and exo norbornene peaks.  The most easily identified norbornene resonances are the alkene hydrogens which can be seen at 6.18-5.90 ppm.  While the ester formation is confirmed by the shift from 4.26 ppm (in complex 2.23) to ~4.75 ppm (in complex 2.24) for the methylene resonances.  It is important to note that the same coupling pattern (ddt) can be seen for the endo methylene resonances of complex 2.24 as was seen for complex 2.8 and 2.18.  The integration of this particular set of methylene peaks shows that the complex was isolated as 65% endo and 35% exo.  There are two impurities that need to be mentioned, water and diethyl ether. The water causes the multiplet at 3.23-2.88 ppm integrates for five protons rather than the expected three and the ether is clearly visible at 1.1 and 3.4 ppm. 58   Figure 2.30: 1H NMR spectrum of complex 2.24 in acetone-d6.   The 13C NMR spectrum also shows incorporation of the norbornene moiety.  The methylene resonance shifted from 50.81 ppm when it was next to an alcohol to 52.51 and 52.10 ppm (endo and exo) with the formation of the ester linkage.  In this spectrum the resonances of the norbornene and alkyne part of the complex show up at almost the same chemical shift as they did for complexes 2.8 and 2.18.  While the rest of the molecule appears very similar to the starting material 2.23 and the impurity persisted in this spectrum as well.  As with complexes 2.8 and 2.18, the different exo and endo peaks are less apparent for the carbons more distant from the norbornene. Unlike the 1H NMR of this compound, the ether did not show up in the 13C Fe+PF6-OClOOOO59  NMR spectrum (Figure 2.31).    Figure 2.31: APT 13C NMR spectrum of complex 2.24 in acetone-d6.    The reaction between the alkyne of complex 2.24 and dicobalt octacarbonyl was performed using the same conditions as for the reactions with complexes 2.8 and 2.18 (Scheme 2.16).  Complex 2.25 was a red solid that was characterized using both IR and NMR spectroscopies.  The IR showed the appearance of the three distinctive bands at ~2100 cm-1 due to the carbonyls coordinated to the cobalt. Fe+PF6-OClOOOO60     Scheme 2.16: Synthesis of complex 2.25.  The 1H NMR spectrum for complex 2.25 shows the downfield shift of the CH2 resonances from 5.05 and 4.75 ppm (complex 2.24) to between 5.40-6.00 ppm (complex 2.25) where some of the resonances overlap with the cyclopentadiene resonance at 5.64 (Figure 2.32). This shift is also seen for the carbon atoms of the methylenes have shifted downfield by approximately 10 ppm (Figure 2.33).   It is interesting to note that the broadened resonance of the CoC≡O carbons at 199 ppm and the broadened alkyne resonances at approximately 91 ppm are visible for this complex.   61   Figure 2.32: 1H NMR spectrum of complex 2.25 in acetone-d6.  62    Figure 2.33: APT 13C NMR spectrum of complex 2.25 in acetone-d6.  Arrows indicate the broadened resonances of the carbon atoms coordinated to cobalt.  2.3.4 Polymerization of norbornene monomer containing a single η6-arene-η5-cyclopentadienyliron(II) moiety and cobalt carbonyl  Polymerization of complex 2.25 using Grubbs’ second generation catalyst was done using the same procedures as for the polymerization of the ferrocene containing complex (2.11) 63  (Scheme 2.17).  Unfortunately, polymer 2.26 proved to be either insoluble or only slightly soluble in most common laboratory solvents including acetone, DCM, acetonitrile, chloroform, THF and DMSO.  In fact, the only solvent that it showed any appreciable solubility was DMF.  Due to the insolubility of this complex no useful NMR spectra could be obtained, however IR did show the continued presence of the cobalt carbonyl bands.  Scheme 2.17: Synthesis of polymer 2.26.  2.4 Molecular weight determination of polymers   The molecular weight of the ferrocene based polymer 2.12 could be determined using GPC, however the η6-arene-η5-cyclopentadienyliron(II) hexafluorophosphate moiety is not 64  compatible with the HPLC column. It was therefore necessary to cleave the cyclopentadienyliron hexafluorophosphate salts from the polymers 2.20 and 2.26 to form their iron free analogues. This was accomplished by dissolving the polymers in a mixture of DMF and acetonitrile (75:25) and irradiating the sample with 300 nm light. The soluble portions of these polymers were then dissolved in THF and analyzed using GPC to give their molecular weight data. The molecular weight of the polymers, before irradiation, was then calculated to give the values presented in Table 2.1.  Unfortunately the iron free analogue of polymer 2.26 was completely insoluble in THF, so no molecular weight data could be obtained.   Table 2.1: Molecular weight data for polymers Polymer Catalyst : monomer  Mw¯¯¯   Mn¯¯¯  PDI 2.12 1:50 49 500 39 600 1.2 2.20* 1:50 55 300 29 800 1.9 * The molecular weights of the polymers are estimated from molecular weights of the soluble portions of their analogs after removal of the cationic cyclopentadienyliron moieties.   2.5  Thermal analysis of polymers  Thermogravimetric analysis of the polymers indicated the the polymers were thermally stable to 125 oC and had 3-4 main degradative steps (Table 2.2).  Polymer 2.12 had four degradative steps, the first one was probably due to the loss of the COs off the cobalt, while the second step was likely due to the loss of the ester. The third degradative step for polymer 2.12 was from 419-472 oC and is the degradation of the ferrocene and the final degradative step from 480-1000 oC would be due to the slow breakdown of the polymer backbone. For the other two 65  polymers, 2.20 and 2.26, the first degradative step which occurred between 125-160 oC, was likely due to the evolution of the CO groups from the alkyne cobalt carbonyl moieties. This loss of the CO groups from the cobalt occurred at a lower temperature for the cationic organoiron polymers (2.20 and 2.26) as compared to the polymers which contained ferrocene (2.12). This difference may be due to destabilization of the cobalt complexes due to the η6-aryl-η5-cyclopentadienyliron(II) hexafluorophosphate salts or could be an effect of the higher molecular weight of the ferrocene polymer. The second degradative step for each polymer occurred from 220-240 oC and was due to the breakdown of the the cyclopentadiene moieties. For polymer 2.20 the third step (417-464 oC) is likely due to the breakdown of the the ester groups while the fourth step (575-802 oC) represents the breakdown of the polymer backbone.  For polymer 2.26 the esters and the backbone both degrade in 3rd step (382-472 oC).  Table 2.2: Thermogravimetric analysis of polynorbornenes. Polymer Step 1 Step 2 Step 3 Step 4 2.12 176-218 oC, 33 % 330-360 oC, 10 % 419-472 oC, 8 % 480-1000 oC, % 2.20 127-148 oC, 8 % 223-232 oC, 11 % 382-472 oC, 57 %  2.26 132-158 oC, 6 % 221-242 oC, 14 % 417-464 oC, 12 % 575-802 oC, 26 %  Differential scanning calorimetry of each polymer indicated that the glass transition temperatures for polymers 2.12 and 2.26 was 61 and 63 oC respectively, while a glass transition temperature could not be found for polymer 2.20 (Table 2.3). Above the glass transition temperature polymer chains can slide past each other when a force is applied. It is therefore important to know the glass transition temperature of polymers as it gives information about the 66  processability and thermal stability of the polymers. For each of the polymers the glass transition temperature changed after the CO had been thermally driven off. For example, in the DSC of polymer 2.26, the evolution of the CO from the polymer was observed from 120-150 oC. A second DSC scan of polymer 2.26 revealed a higher Tg by over 20 oC. This was also seen for polymers 2.12 and 2.20, where the glass transition temperatures were found to be 82 and 84 oC respectively, after loss of the CO.  Table 2.3: Differential scanning calorimetry of polynorbornenes. Polymer Tg Tg* 2.12 61 oC 92 oC 2.20 63 oC 84 oC 2.26 Not found. 82 oC Tg* was taken from a second run, after the CO groups had been removed.  2.6 Cyclic voltammetry of norbornene complexes  Since ferrocene, η6-benzene-η5-cyclopentadienyliron and alkyne-cobalt carbonyl complexes are known to possess electrochemical behaviour, we used cyclic voltammetry to determine if this would be evident in our structures (Table 2.4).  Cyclic voltammetric studies were done on the norbornene complexes, but due to solubility issues were not done on polymers.  The cyclic voltammogram of complex 2.8 displayed an E1/2 = 0.69 V corresponding to the reversible oxidation of the ferrocene moiety to a ferrocinium ion moiety. When complex 2.11 was investigated, both the reversible oxidation of the ferrocene and the irreversible reduction of the cobalt was also seen E1/2 = 0.71 V (ferrocene) and Ep,c = -0.97 V (cobalt). The cyclic 67  voltammogram of complexes 2.18 and 2.24 displayed a reversible redox couples at E1/2 = -1.55 V and E1/2 = -1.27 V respectively, due to the reduction of the cationic η6-benzene-η5-cyclopentadienyliron 18 electron moieties to the neutral 19 e- moieties. The irreversible reduction of the cobalt was seen for complex 2.19 Ep,c = -1.28 V; however, for complex 2.25 the cobalt reduction overlapped with the redox couple of the cationic η6-benzene-η5-cyclopentadienyliron moiety. Two cobalt reduction waves were observed by Arewgoda et al. for smaller alkyne-cobalt carbonyl complexes which ranged from -0.82 V to -1.8 V.{{377 Arewgoda, M. 1982}} However, only one reduction wave was observed for for the alkyne-cobalt carbonyl complexes presented here, this may be due to differences in experimental procedure such as solvent and temperature.   Table 2.4: Cyclic voltammetric studies of norbornene complexes. Complex 1st E1/2 2nd E1/2 Ep,c 2.8 + 0.69   - 1.28 2.11 + 0.71 -0.97 2.18 - 1.55  2.19 - 1.51  2.24 - 1.27  2.25 - 1.30   2.7 Summary A number of neutral and cationic organoiron based norbornene compounds were prepared through esterification with 2-butyne-1,4-diol. The presence of alkyne moieties in these 68  complexes allowed for the generation of mixed organoiron/cobalt norbornene monomers through reaction with dicobalt octacarbonyl. The monomers displayed varying electrochemical properties based on the type of organoiron groups present. The monomer containing ferrocene showed reversible oxidation at E1/2 = + 0.71 V; the monomers containing cationic cyclopentadienyliron moieties displayed a reversible reduction between -1.28 and -1.55 V. The cobalt moieties in these monomers displayed a reduction at -1.30 V, which was reversible for the ferrocene monomer E1/2 = -0.97 V.  The monomers underwent ROMP in the presence of Grubbs’ 2nd generation catalyst to give polynorbornenes containing organoiron and organocobalt moieties in their side chains. The soluble portions of the polymers possessed  Mw¯¯¯ between 49 500 and 55 300 with PDIs between 1.2 and 1.9. The molecular weights of the cationic organoiron polymers were determined from the soluble portions of demetallated samples resulting in lower reported molecular weights. Thermal analysis of the polymers showed that the cobalt units decomposed between 125 oC and 220 oC; the cationic cyclopentadienyliron moieties decomposed between 220 oC and 245 oC. The backbones of the polymers decomposed between 380 oC and 1000 oC.  Differential scanning calorimetry showed that the polymers 2.12 and 2.26 possessed Tgs of 61 oC and 63 oC respectively; interestingly, when the samples were heated above 150 oC and allowed to cool and scanned again the Tgs shifted to higher temperatures (92 oC and 84 oC respectively) presumably due to the decomposition of the cobalt carbonyl moieties. For polymer 2.20 a Tg of 82 oC was only found for after the cobalt carbonyl decomposed. This shift in the glass transition temperature may prove useful in manufacturing as it allows for the control of glass transition post manufacturing.  69  2.8 Detailed experimental All reactions and complexes containing a η6-aryl- η5-cyclopentadienyl iron hexafluorophosphate moiety were kept in the dark to prevent decomposition.  Synthesis of acetylferrocene (2.3)7  Ferrocene (18.16 g, 100 mmol) (2.1), acetic anhydride (53.75 mL, 570 mmol) (2.2), and 4 mL of phosphoric acid were stirred under nitrogen at 100 oC for 20 minutes.  This reaction mixture was then poured into 100 mL of ice and neutralized with the addition of potassium carbonate (~40 g).  An orange precipitate was filtered out of the solution and dried before purification by column chromatography on silica using hexanes to remove residual ferrocene followed by diethyl ether to elute the product.  (14.98 g, 66 % yield) 1H NMR (400 MHz, acetone-d6) δ = 4.77 (NFO t, 2H), 4.52 (NFO t, 2H), 4.22 (s, 5H), 2.35 (s, 3H).  Synthesis of carboxylic acid ferrocene (2.4)7  Acetyl ferrocene (2.3) (5.47 g, 24 mmol), iodine (6.34 g, 25 mmol) and 11 mL of pyridine were stirred for 15 hours under nitrogen.  The reaction was then heated to 100 oC until the solution became viscous (35 minutes) followed by the addition of 180 mL of 0.6 M NaOH.  This mixture was then allowed to stir overnight exposed to the atmosphere.  The reaction mixture was gravity filtered and glacial acetic acid was added to the filtrate until a orange precipitate was formed.  The product was then collected by vacuum filtration as a orange powder that was rinsed with water. 2.56 g, 46 % 1H NMR (400 MHz, acetone-d6) δ = 4.75 (NFO t, 2H), 4.42 (NFO t, 2H), 4.21 (s, 5H).    70   Synthesis of compound 2.6  Carboxylic ferrocene (2.4) (2.4305 g, 9.7 mmol), 2-butyne-1,4-diol (2.5)(4.1709 g, 48 mmol), DCC (2.2515 g, 10.9 mmol), DMAP (1.3090 g, 10.7 mmol), 25 mL DCM and 5 mL DMF were stirred under nitrogen for 5 hours.  The reaction was then cooled to -10 oC and a fine white precipitate of DCU and excess 2-butyne-1,4-diol were filtered out of the solution.  The filtrate was diluted with 150 mL of DCM, washed with 200 mL of 1.2 M HCl solution, dried with MgSO4 and the DCM was removed in vacuo leaving a dark red liquid that was purified using silica chromatography using ether:hexanes 6:4 as the eluent.  The solvent mixture was removed in vacuo leaving a orange-red solid with a 2.1891 g yield (71 % yield). Crystals suitable for X-ray crystallography were grown from ether/hexanes solvent mixture(60/30).  1H NMR (400 MHz, acetone-d6) δ = 4.86 (t, J=1.8, 2H), 4.79 (NFO t, 2H), 4.48 (NFO t, 2H), 4.29 – 4.20 (m, 7H).   1H NMR (400 MHz, CDCl3) δ = 4.84 (t, J=1.8, 2H), 4.82 (NFO t, 2H), 4.41 (NFO t, 2H), 4.30-4.33 (dt, J=6.2, 1.8, 2H), 4.22 (s, 5H), 1.82 (t, J=6.2, 1H).   13C NMR (100 MHz, CDCl3) δ = 171.43, 84.79, 80.95, 71.86, 70.52, 70.09, 52.09, 51.35.   IR 1706 cm-1 (-C=O), 3400 cm-1 (-O-H).  Synthesis of compound 2.7 exo51 In order to fully identify and understand the complexity of the endo-exo mixtures of compounds containing norbornene, the pure 5-norbornene-exo-2-carboxylic acid (2.7 exo) was synthesized according to published procedures.51   1H NMR (400 MHz, CDCl3) δ = 6.15-6.11 (m, 2 H), 3.09 (s, 1 H), 2.92 (s, 1 H), 2.27-2.22 (m, 1 H), 1.93 (dt, J=11.8, 3.9, 1 H), 1.52 (d, J=10.1, 1 H), 1.42-1.35 (m, 2 H). 71   Synthesis of compound 2.8 and 2.8 exo  Compound 2.6 (1.8276 g, 6.1 mmol), 5-norbornene-2-carboxylic acid (2.7 or 2.7 exo) (0.85 mL, 6.9 mmol), DCC (1.4209 g, 6.9 mmol), DMAP (0.7932 g, 6.5 mmol), 15 mL DCM and 3 mL of DMF were stirred under nitrogen for 5 hours.  The reaction was then cooled to -10 oC and a fine white precipitate of DCU  was filtered out of the solution.  The filtrate was diluted with 150 mL of DCM, washed with 200 mL of 1.2 M HCl solution, dried with MgSO4 and the DCM was removed in vacuo leaving an orange solid that was purified using silica chromatography using ether:hexanes 6:4 as the eluent.  The solvent mixture was removed invacuo leaving an orange solid.   2.8  2.0110 g yield (79 % yield).  1H NMR (400 MHz, acetone-d6) δ = 6.23-5.86 (m, 2H), 4.89 (dt, J=3.0, 1.9, 2H), 4.80 (NFO t, 2H), 4.72 (ddt, J= 20.3, 15.9, 1.9, 2H), 4.48 (NFO t, 2H), 4.27 (s, 5H), 3.18 (s, 1H) 3.05-2.94 (m, 1H), 2.88 (s, 1H) 2.25-2.16 (m, 0H), 1.94-1.83 (m, 1H), 1.48 (d, J=8.3 0H), 1.42-1.25 (m, 4H). 13C NMR (101 MHz, acetone-d6) δ = 175.01, 173.88, 170.93, 138.83, 138.44, 136.50, 133.16, 82.43, 82.20, 81.58, 81.44, 72.49, 71.0, 70.98, 70.68, 52.63, 52.25, 52.02, 50.12, 47.35, 46.86, 46.53, 43.69, 43.50, 43.37, 42.40, 30.95, 29.69. IR 1710 cm-1 (C=O). 2.8 exo  (85% yield) 1H NMR (400 MHz, acetone-d6) δ = 6.19 – 6.05 (m, 2H), 4.90 (NFO t, 2H), 4.80 (t, J=1.7, 4H), 4.49 (NFO t, 2H), 4.27 (s, 5H), 3.04-2.75 (m, 3H), 2.21 (dd, J=9.6, 3.7, 1H), 1.93 – 1.82 (m, 1H), 1.48 (d, J=8.3, 1H), 1.41-1.23 (m, 2H). 72   Synthesis of complex 2.9  Complex 2.8 (0.8376 g, 2 mmol) dissolved in 1 mL of DCM was stirred under N2 while Grubbs’ 2nd generation catalyst (0.01709 g, 0.02 mmol in 1 mL DCM) was added to the mixture.  After 30 min the reaction mixture turned viscous and the reaction was quenched with the addition of ethylvinyl ether (1 mmol).  The orange red compound, which had a jelly like appearance, was washed with acetone and dried in a crucible.  The yield appeared to be over 100% possibly due to solvent molecules being trapped in the cross linked polymer.  0.8543 g, 102 % yield.  Synthesis of complexes 2.11 and 2.11 exo  Under N2, 0.8369 g (2 mmol) of complex 2.8 was dissolved in 10 mL dry THF and stirred.  When 0.8442 g (2.5 mmol) of Co2(CO)8 (2.10) was added to the stirring solution CO(g) was evolved.  This evolution of gas lasted for 20 min.  To ensure that the reaction went to completion the reaction was allowed to continue stirring, under N2, for an additional 15 hours.  The solvent was then removed in vacuo leaving a red film which was dissolved in 20 mL of acetone.  After 1 hour of being exposed to the atmosphere, a fine precipitate formed which was filtered out of the solution through Celite.  The filtrate was collected and the solvent removed in vacuo leaving 1.2670 g of the pure complex (2.11). 2.11 1.2670 g yield (90 % yield). 1H NMR (400 MHz, acetone-d6) δ = 6.23 – 5.93 (m, 2H), 5.53 – 5.39 (m, 4H), 4.84 (NFO t, 2H), 4.49 (NFO t, 2H), 4.25 (s, 5H), 3.25 (s, 1H), 3.10 (dt, J=9.3, 4.0, 1H), 2.90 (s, 1H), 2.33 – 2.28 (m, 0H), 2.00-1.89 (m, 1H), 1.59 – 1.26 (m, 3H). 73  13C NMR (101 MHz, acetone-d6) δ = 174.61, 171.72, 138.92, 138.55, 136.52, 133.39, 91.85, 72.39, 71.83, 70.97, 70.63, 65.79, 65.76, 65.56, 65.45, 50.20, 47.34, 46.99, 46.33, 44.00, 43.72, 43.37, 42.43. IR 2106 cm-1, 2067 cm-1 and 2040 cm-1 (CoC≡O) 1718 cm-1 (C=O). 2.11 exo (92 %)  1H NMR (400 MHz, acetone-d6) δ = 6.14 (m, 2H), [5.50 (s),5.49 (d, J=14.3), 5.43 (d, J=14.3), 4H], 4.85 (NFO t, 2H), 4.50 (NFO t, 2H), 4.25 (s, 5H), 3.10 (s, 1H), 2.92 (s, 1H), 2.30 (d, J=8.5, 1H), 1.99 – 1.72 (m, 1H), 1.56 (d, J=8.3, 1H), 1.46 – 1.06 (m, 3H).  Synthesis of polymer 2.12 Under N2, complex 2.11 (1.0565 g, 1.5 mmol) was dissolved in 1 mL of DCM and stirred, Grubbs’ 2nd generation catalyst (0.0257 g 0.03 mmol) dissolved in 1.4 mL of DCM was then added.  After 30 min. 5 mL of methanol was added causing the polymer to precipitate out of solution. The precipitate was collected and triturated with DCM and diethyl ether to remove the lower molecular weight polymers and monomer leaving 0.9972 g of red solid. 1H NMR (400 MHz, CDCl3) δ = 5.48-5.06 (m, 6H), 4.82 (s, 2H), 4.39 (s, 2H), 4.18 (s, 5H), 3.16 (br. s, 1H), 2.95 (br. s, 1H), 2.80 (br. s, 1H), 1.95 (br. s, 2H), 1.76 (br. s, 2H), 1.60 (br. s, 1H), 1.34 (br. s, 1H).  Synthesis of η6-chlorobenzene-η5-cyclopentadienyliron(II) complexes (2.14 a-c)16 A magnetic stir bar, the appropriate arene (2.13 a-c) (277 mmol), ferrocene (2.1) (277 mmol), aluminum (159 mmol) and aluminum chloride (306 mmol) respectively, were placed in a 3-necked 500 mL round bottom flask.  The flask was fitted with a condenser and a thermometer.  74  The reaction was stirred at 135 oC, under nitrogen, in the dark for 5 hours.  The reaction was then allowed to cool to 85 oC before it was poured into 700 mL of ice.  This solution was then filtered through sand in a Buchner funnel.  The filtrate was washed with diethyl ether until the ether layer was a pale yellow colour.  12 g of NH4PF6 was then added to the water layer, resulting in the formation of a green precipitate.  The product was then extracted using DCM and then was washed with water.  The product DCM mixture was dried using magnesium sulphate followed by gravity filtration.  The filtrate was concentrated using a rotary evaporator and then added to diethyl ether forming a yellow precipitate.  The precipitate was collected in a Buchner funnel and dried over vacuum with a 30-45% yield.   2.14 a 1H NMR (400 MHz, acetone-d6) δ = 6.90 (s, 4H), 5.39 (s, 5H). 2.14 b 1H NMR (400 MHz, acetone-d6) δ = 6.81 (d, J=6.1, 2H), 6.57 (t, J=6.0, 2H), 6.46 (t, J=5.8, 1H), 5.30 (s, 5H). 2.14 c 1H NMR (400 MHz, acetone-d6) δ = 6.80 (d, J=6.7, 2H), 6.56 (d, J=6.7, 2H), 5.31 (s, 5H), 2.55 (s, 3H).  Synthesis of complex 2.1652 Complex 2.14 a (3.3044 g, 8 mmol), 4,4-bis(4-hydroxyphenyl)valeric acid (2.15) (1.0353 g, 3.6 mmol), K2CO3 (1.3845 g, 10 mmol) and 40 mL of DMF were combined in a 100 mL round bottom flask with a magnetic stir bar.  The reaction was stirred in a nitrogen environment for 48 hours.  The product was precipitated in 600 mL 1.2 M HCl and NH4PF6 (1.3211 g, 8 mmol).  The pale yellow precipitate was collected in a Buchner funnel and dried over vacuum. Once dry the product was dissolved in 5-10 mL of acetone and a white precipitate was filtered 75  out. The filtrate was then re-precipitated in to 1.2 M HCl , collected in a Buchner funnel and dried over vacuum. This gave  3.2776 g,  87 % yield. 1H NMR (400 MHz, DMSO-d6) δ = 7.38 (d, J=8.9, 4H), 7.28 (d, J=8.9, 4H), 6.81 (d, J=6.9, 4H), 6.42 (d, J=6.9, 4H), 5.28 (s, 10H), 2.46 – 2.38 (m, 2H), 2.12 – 2.04 (m, 2H), 1.68 (s, 3H).  Synthesis of complex 2.17  Complex 2.16 (3.0129 g, 2.9 mmol), 2-butyne-1,4-diol  (2.5) (0.7771 g, 9 mmol), DCC (0.6679 g, 3 mmol), DMAP (0.3741 g, 3 mmol), 15 mL DCM and 5 mL DMF were stirred for 18 hours under nitrogen.  The reaction was then placed in the freezer for 3 h and filtered to remove DCU.  The 60 mL of DCM was added to the filtrate which was then washed with 200 mL of 1.2 M HCl and 6 mmol of NH4PF6.  The organic layer was then was dried using magnesium sulphate followed by gravity filtration.  The DCM was removed from the filtrate using a rotary evaporator, leaving a mixture of product and DCU in DMF.  This mixture was placed in the freezer for 3 hours, resulting in the precipitation of DCU crystals which were then filtered out.  The filtrate was then added to 200 mL of water and 0.9850 g (6 mmol) of NH4PF6 forming a yellow precipitate, which was collected in a Buchner funnel and dried over vacuum.  2.860 g yield (89 % yield). 1H NMR (400 MHz, acetone-d6) δ = 7.48 (t, J=8.8, 4H), 7.34 (d, J=8.7, 4H), 6.82 (d, J=6.6, 4H), 6.52 (d, J=6.3, 4H), 5.38 (s, 10H), 4.71 (s, 2H), 4.23 (s, 2H), 2.60 – 2.50 (m, 2H), 2.29 – 2.19 (m, 2H), 1.76 (s, 3H). 13C NMR (101 MHz, acetone-d6) δ = 172.85, 151.68, 147.61, 133.59, 130.37, 121.09, 104.53, 87.47, 86.58, 80.15, 79.32, 76.68, 52.49, 50.33, 46.02, 36.75, 30.20, 27.68. IR 1738 cm-1 (C=O), 3580 cm-1 (OH) 76   Synthesis of complex 2.18  Complex 2.17 (2.770 g, 2.5 mmol), 5-norbornene-2-carboxylic acid (2.7) (0.35 mL, 2.8 mmol), DCC (0.6680 g 3 mmol), DMAP (0.3741 g, 3 mmol), 15 mL DCM and 5 mL DMF were stirred for 18 hours, in the dark, under nitrogen.  The reaction was then placed in the freezer for 3 h and filtered to remove DCU.  100 mL of DCM was added to the filtrate which was then washed with 100 mL of 1.2 M HCl and 0.9840 g (6 mmol) of NH4PF6.  The organic layer was then was dried using magnesium sulphate followed by gravity filtration.  The DCM was removed from the filtrate using a rotary evaporator, leaving a mixture of product and DCU in DMF.  This mixture was placed in the freezer for 3 hours, resulting in the precipitation of DCU crystals which were then filtered out.  The filtrate was then added to 200 mL of water and 6 mmol of NH4PF6 forming a yellow precipitate, which was collected in a Buchner funnel and dried over vacuum.  2.5166 g yield (82 % yield).   1H NMR (400 MHz, acetone-d6) δ = 7.49 (d, J=7.7, 5H), 7.34 (d, J=7.8, 4H), 6.81 (d, J=5.6, 4H), 6.52 (d, J=5.5, 4H), 6.35 (m, 0H), 6.19-5.87 (m, 2H), 5.38 (s, 10H), 4.76-4.64 (m, 4H), 3.18 (s, 1H), 3.07-2.97 (m, 1H), 2.88 (s, 2H), 2.62-2.50 (m, 2H), 2.30-2.18 (m, 2H), 1.95-1.85 (m, 1H), 1.76 (s, 3H), 1.48 (d, J=8.2, 0H), 1.41-1.26 (m, 3H). 13C NMR (101 MHz, acetone-d6) δ = 175.57, 173.92, 172.96, 152.92*, 152.33, 147.96, 147.51*, 138.92, 138.52, 136.47, 134.01, 133.10, 131.94*, 130.78, 129.85*, 121.44, 119.48*, 105.05, 88.09, 82.05, 81.96, 81.79, 81.60, 81.36, 80.68, 79.17*, 77.45, 76.26*, 52.59, 52.55, 52.16, 50.13, 47.33, 46.87, 46.55, 46.41, 43.68, 43.50, 43.37, 42.40, 37.18, 30.96, 30.53, 29.74, 27.98.*denotes starting material peaks. IR 1733 cm-1,1730 cm-1 (C=O) 77   Syntheis of complex 2.19 Under N2, 0.8585 g (2.5 mmol) of dicobalt octacarbonyl (2.10) was added to a stirring solution of 2.3331 g (1.9 mmol) of complex 2.18 in 10 mL of THF.  For the first 30 min, bubbles appeared in the reaction flask indicating the evolution of carbon monoxide from the reaction.  To ensure the full incorporation of the cobalt, the reaction was stirred for an additional 14 hours.  The THF was removed in vacuo leaving a red residue that was dissolved in acetone and allowed to sit on the bench top until a small amount of precipitate formed (30 min - 1 hour).  The solution was then filtered through Celite and the acetone was concentrated to ~5 mL in vacuo.  The solution was then added to 200 mL of water containing 0.3280 g NH4PF6, forming a pink precipitate that was collected and dried for 24-48 hours over vacuum. 2.5889 g yield (90 % yield). 1H NMR (400 MHz, acetone-d6) δ = 7.48 (d, J=8.6, 4H), 7.33 (d, J=8.6, 4H), 6.81 (d, J=6.4, 4H), 6.51 (d, J=6.6, 4H), 6.23 – 5.92 (m, 2H), 5.48 – 5.17 (m, 14H), 3.23 (s, 1H), 3.15-3.04 (m, 1H), 2.90 (s, 1H), 2.66 – 2.52 (m, 2H), 2.37 – 2.18 (m, 2H), 2.01 – 1.88 (m, 1H), 1.73 (s, 4H), 1.54 (d, J=7.9, 0H), 1.49 – 1.22 (m, 4H). 13C NMR (101 MHz, acetone-d6) δ = 173.49, 152.41, 147.95, 138.96, 138.60, 136.47, 134.01, 133.35, 130.69, 121.40, 105.12, 88.03, 80.64, 77.42, 65.50, 65.40, 65.38, 50.21, 47.33, 47.00, 46.35, 46.33, 44.00, 43.73, 43.36, 42.96, 42.43, 37.29, 31.06, 30.62,  27.87. The alkyne and carbonyl carbons coordinated to the cobalt cannot be seen due to broadening, also the two endo and exo carbonyl carbons of the norbornene are not visible. IR 2100 cm-1, 2067 cm-1 and 2034 cm-1 (CoC≡O) 1725 cm-1 (C=O)    78  Synthesis of polymer 2.20   For the synthesis of the polymers all chemicals and solvents were kept under nitrogen.  0.0257 g of 2nd generation Grubbs catalyst dissolved in 1.4 mL of dry DCM was added to complex 2.19 (2.2701 g, 1.5 mmol) dissolved in 2 mL of dry DCM and stirred.  After 45 minutes, the polymer had precipitated out of solution and 5 mL of ethylvinyl ether was added to the reaction mixture to terminate any residual polymer growth, end capping the polymers.  The polymer was then triturated with DCM to remove any residual monomer leaving higher molecular weight polymers in a 2.2107 g yield 1H NMR (400 MHz, DMSO-d6) δ = 7.35 (bs, 4H), 7.25 (bs, 4H), 6.80 (bs, 4H), 6.40 (bs, 4H), 5.28 (bs, 16H), 2.18 (bs, 1H), 1.66 (bs, 3H), 1.23 (bs, 6H). 13C NMR: not soluble enough to obtain.  Synthesis of complex 2.22 (modified procedure from reference 50 ) Complex 2.14 a (3.3249 g, 8 mmol), 4-hydroxy benzoic acid (2.21) (4.4081 g, 32 mmol) (19), K2CO3 (11.0437 g, 80 mmol) and 65 mL of DMF were combined in a 100 mL round bottom flask with a magnetic stir bar.  The reaction was stirred in a dark nitrogen environment for 18 hours.  The reaction mixture was then poured into 300 mL 1.2 M HCl and NH4PF6 (8 mmol).  The product DCM mixture was dried using magnesium sulphate followed by gravity filtration.  The filtrate was concentrated using a rotary evaporator and then added to diethyl ether forming a yellow precipitate.  The pale yellow precipitate was collected in a Buchner funnel and dried over vacuum.  3.5058 g yield (85 % yield).    1H NMR (400 MHz, acetone-d6) δ = 8.19 (d, J=8.8, 2H), 7.47 (d, J=8.8, 2H), 6.90 (d, J=7.0, 2H), 6.66 (d, J=6.9, 2H), 5.44 (s, 5H). 79   Synthesis of complex 2.23  Complex 2.22 (4.9393, 9.58 mmol), 2-butyne-1,4-diol (2.5) (45 mmol), DCC (2.2075 g, 10.6 mmol), DMAP (1.2282 g, 10 mmol), 30 mL DCM and 10 mL DMF were stirred for 18 hours under nitrogen and in the dark.  The reaction was then placed in the freezer for 3 h and filtered to remove DCU.  100 mL of DCM was added to the filtrate which was then washed with 200 mL of 1.2 M HCl and 1.64 g (10 mmol) of NH4PF6.  The organic layer was was dried using magnesium sulphate followed by gravity filtration.  The DCM was removed from the filtrate using a rotary evaporator, leaving a mixture of product and DCU in DMF.  This mixture was placed in the freezer for 3 hours, resulting in the precipitation of DCU crystals which were then filtered out.  The filtrate was then added to 200 mL of water and 4 mmol of NH4PF6 forming a yellow precipitate, which was collected in a Buchner funnel and dried over vacuum.  4.9724 g yield (89 % yield). 1H NMR (400 MHz, acetone-d6) δ = 8.17 (d, J=8.8, 2H), 7.46 (d, J=8.8, 2H), 6.84 (d, J=6.8, 2H), 6.61 (d, J=6.8, 2H), 5.39 (s, 5H), 5.01 (t, J=1.8, 2H), 4.26 (t, J=1.8, 2H). 13C NMR (101 MHz, acetone-d6) δ = 165.51, 158.95, 133.52, 132.66, 131.19*, 128.74, 121.55, 121.37*, 105.83, 88.41, 88.30*, 87.55, 81.16, 81.01* 79.43, 79.03, 78.14* 53.89, 50.81. * denotes impurity peaks. IR 1720 cm-1 (C=O), 3398 cm-1 (OH)  Synthesis of complex 2.24 Complex 2.23 (4.8524 g 8.3 mmol), 5-norbornene-2-carboxylic acid (1.6 mL, 13 mmol) (2.7), DCC (2.9005 g, 14 mmol), DMAP (1.5336 g, 12.5 mmol), 15 mL DCM and 5 mL DMF 80  were stirred for 18 hours, in the dark, under nitrogen.  The reaction was then placed in the freezer for 3 h and filtered to remove DCU.  150 mL of DCM was added to the filtrate which was then washed with 1.4765 g (9 mmol) of NH4PF6 dissolved in 200 mL of 1.2 M HCl and once with 200 mL of 1.2 M HCl.  The organic layer was then was dried using magnesium sulphate followed by gravity filtration.  The DCM was removed from the filtrate in vacuo, leaving a mixture of product and DCU in DMF.  This mixture was placed in the freezer for 3 hours, resulting in the precipitation of DCU crystals which were then filtered out.  The filtrate was then added to 150 mL of diethyl ether forming a brown viscous oil which was isolated by decanting off the DMF/ether and allowing to dry for 24 hours.  2.073 g yield (36 % yield). 1H NMR (400 MHz, acetone-d6) δ = 8.18 (d, J = 8.4, 2H), 7.48 (d, J = 8.5, 2H), 6.87 (d, J = 6.5, 2H), 6.64 (d, J = 6.5, 2H), 6.18-5.90 (m, 2H), 5.42 (s, 5H), 5.11-5.02 (m, 2H), 4.81 (t, J=1.8, 0H), 4.73 (ddt, J= 23.65, 15.9, 1.8, 1H), 3.23-2.88 (m, 5H), 2.28 – 2.18 (m, 0H), 1.97-1.84 (m, 1H), 1.52 – 1.23 (m, 3H). 13C NMR (101 MHz, acetone-d6) δ = 175.55, 173.89, 165.16, 158.71, 138.88, 138.46, 136.46, 133.32, 133.10, 132.45, 130.96*, 128.41, 121.37, 121.18*, 105.60, 105.34*, 88.25, 88.13, 82.40, 82.30, 81.39*, 81.15, 80.97*, 80.80, 78.85, 77.90*, 53.42, 52.53, 52.13, 50.10, 47.32, 46.83, 46.53, 43.66, 43.48, 43.36, 42.41, 30.93, 29.65.  * denotes slight impurities IR 1728 cm-1 (C=O).  Synthesis of complex 2.25  Under N2, 0.9961g (2.9  mmol) of dicobalt octacarbonyl (2.10) was added to a stirring solution of 1.7710 g  (2.5 mmol) of complex 2.24 in 10 mL of THF.  For the first 30 min, bubbles appeared in the reaction flask indicating the evolution of carbon monoxide from the 81  reaction.  To ensure the full incorporation of the cobalt the reaction was stirred for an additional 12.5 hours.  The THF was removed in vacuo leaving a red residue that was dissolved in acetone and allowed to sit on the bench top until a small amount of precipitate formed (20-30 min).  The solution was then filtered through celite and the acetone was concentrated to 5 mL in vacuo.  The solution was then added to water containing NH4PF6 forming a pink precipitate that was collected.  2.3418 g yield (95 % yield). 1H NMR (400 MHz, acetone-d6) δ = 7.48 (d, J=8.6, 4H), 7.33 (d, J=8.6, 4H), 6.81 (d, J=6.4, 4H), 6.50 (d, J=6.5, 4H), 6.21-5.92 (m, 2H), 5.48 – 5.17 (m, 14H), 3.23 (s, 1H), 3.08 (s, 1H), 2.89 (s, 1H), 2.58 (s, 2H), 2.30 (s, 3H), 1.99-1.87 (m, 2H), 1.78-1.70 (m, 4H), 1.52 (d, 1H), 1.47-1.23 (m, 5H), 0.98 – 0.80 (m, 2H). 13C NMR (101 MHz, acetone-d6) δ = 200.31, 165.83, 158.96, 138.95, 138.57, 136.48, 133.27, 132.82*, 132.21, 130.99*, 128.61, 122.73*, 120.96, 105.71, 91.88, 91.16, 88.27, 88.09*, 80.98, 80.77*, 79.21, 77.83*, 66.55, 65.53, 65.43, 50.20, 47.32, 46.98, 46.32, 43.98, 43.70, 43.36, 42.42, 30.95, 29.64.  * denotes slight impurities IR 2103 cm-1, 2067 cm-1 and 2033 cm-1 (CoC≡O) 1720 cm-1 (C=O).  Synthesis of polymer 2.26  For the synthesis of the polymers all chemicals and solvents were kept under nitrogen.  0.0257 g of 2nd generation Grubbs catalyst dissolved in 1.4 mL of dry DCM was added to 1.4831 g (1.5 mmol) complex 2.25 dissolved in 2 mL of dry DCM and stirred.  After 30 minutes 5 mL of ethylvinyl ether was added to the reaction mixture to terminate polymer growth and endcap the polymers.  The polymer was then precipitated into ether, collected by vacuum filtration and allowed to dry over vacuum for 24 hours giving a 1.3644 g yield. 82  IR 2103 cm-1, 2067 cm-1 and 2033 cm-1 (CoC≡O) 1722 cm-1 (C=O).  83  Chapter 3:   Methacrylate based polymers 3.1 Introduction There is a plethora of literature and commercial examples of polymers based on the polymerization of methacrylic esters (Figure 3.1). The simplest of these would be poly(methylmethacrylate) which was first synthesized in the 1880’s by Fittig and Paul.53 Methacrylates can be polymerized using anionic chain polymerization and radical polymerization.54 The anionic methods require very pure monomer and stringently purified and degassed solvents. Radical polymerization is more robust allowing for the use of monomers with trace impurities. Radical scavengers such as oxygen can cause premature chain termination; however, if enough initiator is added, polymers can be obtained even in the presence of trace amounts of oxygen or without the removal of the stabilizers present in commercially available monomers.    Figure 3.1: General polymerization of methacrylates. Radical polymerization occurs in three steps: initiation, propagation and termination (Figure 3.2). Initiation involves a reaction that produces radicals.  This is often achieved using peroxides or alkyl azo compounds. For example AIBN is an excellent source of radicals through its thermal or photochemical decomposition (Figure 3.3). Propagation is the process by which a radical reacts with monomer to give a radical product. Termination is when two radical species 84  come together to make a single non-radical product. This could be two radical polymer ends or a radical polymer end and an initiator radical. InitiationPropagationTerminationX2 X• + X•R+ X•RX•RX•R+R•RXnnR•RXn2 XRXnorR•RXn+ X•XRXnR=O O Figure 3.2: Initiation, propagation and termination of methylmethacrylate radical polymerization. 85   Figure 3.3: Production of radicals from AIBN.  The incorporation of various types of organoiron into methacrylate polymers has been studied mainly by Pittman et al and Abd-El-Aziz et al.55-66  In the 1970s, Pittman et al. reported on the synthesis of methacrylate polymers containing ferrocene (Figure 3.4, complex a).  The main goal of their research was to make charge transfer polymers. To this end, the ferrocene polymers were treated with tetracyanoethylene, dichlorodicyanoquinone, and chloranil.58-62  Unfortunately, the ferrocene polymers were not shown to have any charge transfer properties.  Previous work done by Abd-El-Aziz et al. has shown that AIBN can be used to prepare polymethacrylates with η6-aryl-η5-cyclopentadienyliron(II) hexafluorophosphate groups in their side chain (Figure 3.4, complexes b and c).64, 66-68  It is important to note that the presence of the cationic cyclopentadienyliron was found to increase the solubility of these polymers, which would increase their processability. 86   Figure 3.4: Sample of methacrylates which contain organoiron moieties.  This chapter describes the synthesis of methacrylic ester based organoiron/cobalt polymers. Unlike chapter 2 the cobalt was incorporated into these molecules post polymerization the reason for this will be discussed herein. The present work builds on both the previous research in the Abd-El-Aziz lab, as well as, the previous chapter of this thesis by showing that alkyne coordinated dicobalt hexacarbonyl can also be incorporated into polymethacrylates containing organoiron (post-polymerization).  In this chapter three different classes of polymethacrylates were synthesized, one with neutral ferrocene and cobalt carbonyl-alkyne moieties and two containing cationic η6-aryl-η5-cyclopentadienyliron(II) and cobalt carbonyl-alkyne moieties. 87  3.2  Synthesis and characterization of ferrocene and cobalt containing polymethacrylates 3.2.1 Synthesis of a methacrylate monomer that contains ferrocene  Synthesis of the methacrylate ferrocene complex 3.2 was accomplished through Steglich esterification between methacrylic acid (3.1) and the alcohol of complex 2.6 (Scheme 3.1).  After purification by column chromatography, the complex was isolated as an orange oil.  Scheme 3.1: Synthesis of complex 3.2.  The 1H NMR spectrum of complex 3.2 (Figure 3.5) shows the appearance of the diastereotopic protons of the terminal olefin carbon at 6.14 and 5.58 ppm as well as the appearance of the methyl resonance at 1.92 ppm.  Upon closer inspection, the methylene protons of the butyne unit nearest to the newly formed ester have shifted from 4.32 ppm to 4.80 ppm (Figure 3.6). One can also see that these methylene protons are no longer coupled to the alcohol proton going from a doublet of triplets (when in CDCl3) to a triplet.  88   Figure 3.5: 1H NMR spectrum of complex 3.2 in CDCl3. 89   Figure 3.6: 1H NMR spectral comparison for complexes 2.6 and 3.2 in CDCl3. The incorporation of the methacrylate moiety can also be seen in the 13C NMR spectrum of complex 3.2 (Figure 3.7).  The carbonyl carbon of the newly formed ester can be seen at 167 ppm, the quaternary carbon appears at 136 ppm, the methylene carbon is at 127 ppm and the methyl resonance is at 18.5 ppm.  Identification of these resonances was determined through analysis of the HMBC and HSQC spectra for complex 3.2 (Figure 3.8 and Figure 3.9 respectively).  The HMBC spectrum also shows that there is connectivity between one of the carbonyl carbons to the methyl of the methacrylate and the methylene on the other side of the newly formed ester. This connectivity allowed for the identification of the two carbonyl carbons.  90   Figure 3.7: APT 13C NMR spectrum of complex 3.2 in CDCl3. 91   Figure 3.8: HMBC NMR spectrum of complex 3.2 in CDCl3.  Resonance indicating connectivity between the carbonyl of the methacrylate and the methylene on the other side of the ester is indicated by the arrow. 92   Figure 3.9: HSQC NMR spectrum of 3.2 in CDCl3.  3.2.2 Synthesis of a model methacrylate complex that contains both ferrocene and cobalt carbonyl  Cobalt carbonyl was added across the triple bond in a THF solution to make the model complex 3.3 (Scheme 3.2).  This complex was isolated as a red crystalline solid that was characterized through IR, NMR spectroscopies and X-ray crystallography.  93   Scheme 3.2: Synthesis of complex 3.3. The IR for complex 3.3 shows three characteristic bands for the C≡O stretch at 2096, 2053 and 2022 cm-1, indicating that there is some cobalt carbonyl in the sample.  There is also no alkyne stretching band or bridging carbonyl band visible in the spectrum.  The 1H NMR spectrum of complex 3.3 can be seen in Figure 3.10 where the methylene resonances have shifted downfield to 5.51 and 5.54 ppm.  This downfield shift is due to the deshielding effects of the cobalt and was accompanied with a loss of coupling between the two methylenes.  The 13C NMR spectrum also shows a downfield shift of the methylenes to two very close peaks at 65.8 ppm (Figure 3.11).  Also the alkyne carbons are now resonating together at 91.7 ppm as a broadened peak due to the broadening effect of the cobalt.    94   Figure 3.10: 1H NMR spectrum of complex 3.3 in acetone-d6. OOOOFeCoOCCOOCCoOCCOOC95   Figure 3.11: APT 13C NMR spectrum of complex 3.3 in acetone-d6.  Complex 3.3 formed beautiful red crystals that were characterized through X-ray crystallography.  As can be seen in Figure 3.12 there is coordination between the acetylene carbons and each cobalt atom.  This pseudo saw horse structure is similar to typical M2L6-acetylenes.69  The pseudo saw horse structure has a nearly linear dihedral C21-Co1-Co2-C24 angle (6o) and a Co-Co bond length of 2.48 Å, that lie within normal ranges for this type of structure.  The bulkiness of the cobalt carbonyl cluster forces the rest of the molecule into a pseudo cis formation at the acetylene moiety leaving the methylene carbons (C15 and C12) and ester atoms in a parallel orientation where they are nearly in the same plane.  The alkyne C13-OOOOFeCoOCCOOCCoOCCOOC96  C14 bond (1.338 Å) and the C-C≡C-C “bend back” angles (142.47o and 143.25o) were fairly typical.70  Figure 3.12: ORTEP diagram for complex 3.3.  Attempts to polymerize complex 3.3 using AIBN was unsuccessful.  This failure was likely due to a radical reaction involving the cobalt carbonyl.  The 1H-NMR of the products showed a complicated spectrum with inadequate characterization data.   Complex 3.3 was useful as a model complex for alkyne dicobalt hexacarbonyl complexes indicating the effect of the cobalt on NMR resonances.  3.2.3 Polymerization of a ferrocene-containing methacrylate monomer  While attempts to polymerize complex 3.3 were unsuccessful, the precursor compound 3.2 was easily polymerized using AIBN (Scheme 3.3).  The best conditions for this polymerization proved to be in dry DMF using 7:1 monomer to AIBN ratio.  The successful 97  polymerization of compound 3.2 was confirmed through GPC and NMR spectroscopy. The molecular weight of the polymer will be discussed in section 3.4.  Scheme 3.3: Synthesis of polymer 3.4.   The 1H NMR spectrum of polymer 3.4 indicates that the polymerization was successful (Figure 3.13).  All of the resonances have broadened as is typical for polymer spectra and there is no longer any evidence of the olefin hydrogen atoms of the methacrylate at 6.14 and 5.58 ppm.  98   Figure 3.13: 1H NMR spectrum of polymer 3.4 in CDCl3.  3.2.4 Coordination of cobalt carbonyl to a ferrocene-containing methacrylate polymer  The incorporation of cobalt into the polymer was achieved by first dissolving polymer 3.4 into THF and adding dicobalt octacarbonyl (Scheme 3.4).  Converting the polymer from an orange color to a dark red color.  The incorporation of the cobalt can be seen through IR and NMR.  For IR 3 characteristic bands appear at 2023, 2054 and 2096 cm-1 representing the C≡O bonds of the cobalt carbonyls.  1H NMR confirms the full incorporation of the cobalt into the polymer with the shift of the methylene hydrogens from 4.65 and 4.85 ppm to 5.04 and 5.35 ppm respectively (Figure 3.14). OOOOFen99   Scheme 3.4: Synthesis of polymer 3.5. 4.24.54.85.15.45.7 ppm12 3.43.5 Figure 3.14: 1H NMR spectral comparison of polymers 3.4 and 3.5 in CDCl3.   100  3.3 Synthesis and characterization of a polymethacrylate containing η6-arene-η5 -cyclopentadienyliron and cobalt carbonyl 3.3.1 Synthesis of a methacrylate monomer containing two η6-arene-η5-cyclopentadienyliron(II) moieties  The first step in the synthesis of a polymethacrylate polymer containing containing two η6-arene-η5-cyclopentadienyliron hexafluorophosphate moieties and alkyne coordinated cobalt carbonyl was to react complex 2.17 with methacryloyl chloride (3.6) (Scheme 3.5).  As polymerization of methacrylate monomers can be both thermal- and photo-initiated this complex was carefully kept in a cool dark place. 101   Scheme 3.5: Synthesis of complex 3.7.  The full incorporation of the methacrylate is evidenced in the 1H NMR and 13C NMR spectra. The 1H NMR spectrum shows the appearance of methacrylate resonances at 1.92, 5.70 and 6.09 ppm as well as the shift of the methylene groups adjacent to the alkyne from 4.22 and 102  4.71 ppm (complex 2.17) to 4.74 and 4.84 ppm (complex 3.7) (Figure 3.15). The 13C NMR spectrum also shows the four methacrylate resonances at 164.06, 136.83, 126.70 and 18.39 ppm (Figure 3.16).  Figure 3.15: 1H NMR spectrum of complex 3.7 in acetone-d6.   103   Figure 3.16: APT 13C NMR spectrum of complex 3.7 in acetone-d6.  3.3.2 Polymerization of a methacrylate monomer containing two η6-arene-η5-cyclopentadienyliron(II) moieties Radical polymerization of complex 3.7 was initiated with AIBN, giving polymer 3.8 (Scheme 3.6).  The polymerization was confirmed using 1H NMR spectroscopy, which shows the disappearance of the olefin peaks of the methacrylate monomer and broadening of all resonances (Figure 3.17). 104   Scheme 3.6: Synthesis of polymer 3.8. 105   Figure 3.17: 1H NMR spectrum of polymer 3.8 in acetone-d6.  3.3.3 Coordination of cobalt carbonyl to a methacrylate polymer containing two η6-arene-η5-cyclopentadienyliron(II) moieties The incorporation of cobalt into the polymer was achieved by first dissolving polymer 3.8 into a THF/DMF mixture and adding dicobalt octacarbonyl (Scheme 3.7), which converted the polymer from a yellow colour to a pink colour.  The incorporation of the cobalt was seen with the appearance of the three characteristic IR bands at 2098, 2057 and 2026 cm-1 representing the carbonyl groups off the cobalt.  The 1H NMR spectrum indicates that the cobalt was not fully incorporated into the polymer (Figure 3.18). The resonances due to the methylenes 106  adjacent to alkynes which are complexed to cobalt have shifted to beneath the cyclopentadiene peak, increasing its integration to ~12. The other methylenes which are not influenced by the cobalt remain at ~4.7 ppm. The integrations of these peaks suggest that the cobalt was incorporated into approximately half of the alkyne units of the polymers.    107   Scheme 3.7: Synthesis of polymer 3.9. 108   Figure 3.18: 1H NMR spectral comparison of polymers 3.8 and 3.9 in acetone-d6.  3.3.4 Synthesis of a methacrylate monomer containing a single η6-arene-η5-cyclopentadienyliron(II) moiety  The first step in the synthesis of a polymethacrylate polymer containing containing a single η6-arene-η5-cyclopentadienyliron moiety and cobalt carbonyl was to react complex 2.23 with methacryloyl chloride (3.6) (Scheme 3.8).  As polymerization of methacrylate monomer can be initiated both thermally and photically this complex was carefully kept out of the light. 109     Scheme 3.8: Synthesis of complex 3.10.  The 1H NMR spectrum of complex 3.10 appeared as expected for this type of molecule (Figure 3.19).  The methacrylate resonances are found at 6.11, 5.72 and 1.92 ppm.  The success of the esterification reaction is indicated by the shift of the methylene resonances from 4.26 and 5.01 ppm (complex 2.23) to 4.88 and 5.06 ppm (complex 3.10). The sample was not completely pure as it contained a small amount of DCU  from the previous reaction and a small amount of starting material.  The DCU appeared from 1.00-1.90 ppm and at 2.27 ppm and some starting material is apparent as small peaks in the aromatic and complexed aromatic regions. 110   Figure 3.19: 1H NMR spectrum of complex 3.10 acetone-d6.  The 13C NMR spectrum for complex 3.10 also shows the appearance of the four resonances due to the methacrylic ester at 166.01, 136.87, 126.74 and 18.39 ppm (Figure 3.20).  The carbon resonance of one of the methylenes was also seen to shift from 53.89 and 50.81 ppm for complex 2.23 to 53.31 and 52.79 ppm for complex 3.10.  The residual DCU and starting material that were seen in the 1H NMR spectrum are even more obvious in the 13C NMR spectrum.  The very small amount of starting material resonates as peaks adjacent to the aromatic peaks while the DCU has resonances at 31.98, 30.76, 26.12, 25.42, 25.20 and 24.69 ppm. 111   Figure 3.20: APT 13C NMR spectrum of complex 3.10 in acetone-d6.  3.3.5 Polymerization of a methacrylate monomer containing a single η6-arene-η5-cyclopentadienyliron(II) moiety  Radical polymerization of complex 3.10 was initiated with AIBN, giving polymer 3.11 (Scheme 3.9).  The molecular weight of this polymer was not determined directly due to the incompatibility of the cationic cyclopentadienyliron unit with the GPC column, however the polymerization was confirmed using NMR spectroscopies.  The 1H NMR spectrum (Figure 3.21) shows that the olefinic peaks of the methacrylate monomer have disappeared as well as a broadening of the resonances as is typical for polymers. 112   Scheme 3.9: Synthesis of polymer 3.11. 113   Figure 3.21: 1H NMR spectrum of polymer 3.11.  3.3.6 Coordination of cobalt carbonyl to a methacrylate polymer monomer containing a single η6-arene-η5-cyclopentadienyliron(II) moiety  Polymer 3.11 was reacted with cobalt carbonyl in a THF/DMF solution, giving polymer 3.12 (Scheme 3.10).  It was more difficult to purify and analyze this polymer then previously mentioned cobalt containing complexes due to insolubility issues.  The IR spectrum for this compound showed peaks at 2103, 2063 and 2032 cm-1 indicating partial incorporation of the cobalt carbonyl; however, these bands were not as intense as in the previous cobalt-containing 114  polymers. The IR spectrum also lacked a peak at ~1830 cm-1 for the bridging carbonyls of dicobalt octacarbonyl.  Scheme 3.10: Synthesis of polymer 3.12.  3.4 Molecular weight determination of polymers    As in chapter 2 the ferrocene based polymer could be put directly into the GPC, while the organic analogues of complexes 3.8 and 3.11 needed to be made (Table 3.1). For the ferrocene polymer 3.4 the  Mw¯¯¯ = 19 100 and  Mn¯¯¯ = 15 200, which is approximately 52 and 42 monomeric units respectively.  Pyrolysis at 200 oC was used to remove the cationic cyclopentadienyliron from polymers 3.8 and 3.11, where the soluble portions of the polymers were then analyzed by 115  GPC. The molecular weights of the organic analogues were then used to calculate the molecular weight of the ferrocene and cobalt containing polymer. At best the soluble portions of these polymers can be called oligomers having  Mw¯¯¯ s and  Mn¯¯¯ s ranging from 2 - 9 monomeric units.  Unfortunately the soluble portions of the polymer analogues were only 5 - 7 % of the polymer that was pyrolysed, suggesting that higher molecular weight polymers were produced as well.   Table 3.1: Molecular weight data for polymers Polymer  Mw¯¯¯ , units  Mn¯¯¯ , units PDI 3.4 19 100, 52 15 200, 42 1.3 3.5** 33 900 27 400 1.3 3.8* 3 244, 3 2 342, 2 1.4 3.11*  5 840, 9 5 266, 8 1.1 * The molecular weights of the polymers are estimated from molecular weights of the soluble portions of their analogs after removal of the cationic cyclopentadienyliron moieties. ** Estimated from the molecular weight of the cobalt carbonyl free precursor polymer.  3.5 Thermal analysis of polymers Thermal analysis of polymers was conducted using TGA and DSC. The TGA data for the polymers is tabulated in  Table 3.2. It can clearly be seen that the cationic organoiron polymers 3.8 and 3.11 began degrade at between 215 and 250 °C due to the decomposition of the cation iron moiety. The cobalt containing analogue 3.9 showed the decomposition of the alkyne-hexacarbonyldicobalt moieties at 120 – 200 °C.  For compound 3.12 there was little evidence of the evolution of the 116  carbonyl groups, this is likely due to only having partial inclusion of the cobalt carbonyl. The ferrocene based polymers were stable up to 263 °C (3.4) and 138 °C (3.5) due to the decomposition of the ester and alkyne-hexacarbonyldicobalt respectively.   Table 3.2: Thermogravimetric analysis of polymermethacrylates. Polymer Step 1 (oC), % Step 2 (oC), % Step 3 (oC), % Step 4 (oC), % 3.4 263 – 309, 14 % 371 – 446, 22% 622 – 673, 9.1 %  3.5 138 – 189, 10 % 354 – 526, 64 %   3.8 216 – 247, 21 % 502 – 576, 47 % 600 – 900, 10%  3.9 120-200, 4 % 216 – 251, 10% 320 – 383, 20 % 400 – 900, 12% 3.11 218 – 250, 29 % 940 – 994, 12 %   3.12 209 – 246, 15 % 407 – 445, 17 % 707 – 780, 8 %   Differential scanning calorimetry showed that the polymers displayed glass transition temperatures between 78 and 138 °C (Table 3.3). No glass transition temperatures could be found for the alkyne-hexacarbonyldicobalt containing polymers until after the carbonyl groups had been thermally driven off.     117  Table 3.3: Differential scanning calorimetry of organoiron polymethacrylates. Polymer Tg (oC) Tg* (oC) 3.4 78  3.5 Not found 92 3.8 86  3.9 Not found 92 3.11 130  3.12 Not found 138 Tg* was taken from a second run, after the CO groups had been removed.  3.6 Summary A number of polymethacrylates containing two different organometallic moieties were prepared. The polymers possessed a combination of either ferrocene and Co2(CO)6 or cationic cyclopentadienyliron moieties and Co2(CO)6. They were prepared by coordinating Co2(CO)6 with pre-prepared organoiron polymethacrylates containing alkyne moieties. The cobalt moieties were added post polymerization since the alkyne Co2(CO)6 complexes were found to be incompatible with radical polymerization. Gel permeation chromatography indicated that the polymers possessed MWs between 3 244 and 33 900, with PDIs between 1.1 and 1.4.  Thermal analysis showed the polymers displayed glass transition temperatures between 78 and 138 °C.    118  3.7 Detailed experimental All reactions and complexes containing a η6-aryl- η5-cyclopentadienyl iron hexafluorophosphate moiety were kept in the dark to prevent decomposition.  Synthesis of complex 3.2  Compound 2.6 (1.087 g, 3.4 mmol), methacrylic acid (3.1) ( 0.40 mL, 4.7 mmol), DCC (0.8145 g, 3.95 mmol), DMAP (0.4893 g, 4 mmol), 15 mL DCM were stirred under nitrogen for 18 hours.  The reaction was then cooled to -10 oC and a fine white precipitate of DCU was filtered out of the solution.  The filtrate was diluted with 150 mL of DCM, washed with 200 mL of 1.2 M HCl solution, dried with MgSO4 and the DCM was removed in vacuo leaving a orange liquid that was purified using silica chromatography using ether:hexanes 6:4 as the eluent.  The solvent mixture was removed in vacuo leaving an orange liquid with a yield of 0.8851 g (71 % yield). 1H NMR (400 MHz, CDCl3) δ = 6.14 (dq, J=1.6, 1.0, 1H), 5.58 (p, J=1.6, 1H), 4.84 (t, J=1.8, 2H), 4.82 (NFO t, J=1.9, 2H), 4.80 (t, J=1.8, 2H), 4.40 (NFO t, J=1.9, 2H), 4.22 (s, 5H), 1.92 (dd, J=1.5, 1.0, 3H).  1H NMR (400 MHz, acetone) δ = 6.10 (dq, J=1.6, 1.0 1H), 5.67 (p, J=1.6, 1H), 4.90 (t, J=1.8, 2H), 4.87 (t, J=1.8, 2H), 4.80 (NFO t, J=1.9, 2H), 4.48 (NFO t, J=1.9, 2H), 4.26 (s, 5H), 1.91 (dd, J=1.5, 1.0 3H) 13C NMR (101 MHz, CDCl3) δ = 171.27, 166.76, 135.77, 126.82, 81.69, 80.56, 71.85, 70.50, 70.08, 69.95, 52.63, 51.88, 18.49. IR 1714 cm-1 (C=O)     119  Synthesis of complex 3.3 In a N2 environment, complex 3.2 (0.3676 g, 1 mmol) was dissolved in THF and 0.4205 g (1.2 mmol) of Co2(CO)8 (2.10)  was added to this stirring solution.  Upon the addition of Co2(CO)8, the solution turned from orange to red accompanied with the evolution of CO from the solution.  After 1 hour the evolution of CO2 stopped.  However, the solution was allowed to stir for an additional 5-12 hours to ensure the full incorporation of the cobalt.  The THF was removed in vacuo and the red residue was dissolved in 100 mL of acetone, after 5 min a small amount of brown precipitate formed, which was filtered from the solution.  The acetone was then removed in vacuo leaving 0.6299 g (97 % yield) of a dark red solid.  Crystals suitable for X-ray diffraction were then grown by slow evaporation from acetone. 1H NMR (400 MHz, acetone-d6) δ = 6.20 (dq, J=1.6, 1.0, 1H), 5.71 (p, J=1.6, 1H), 5.54 (s, 2H), 5.51 (s, 2H), 4.85 – 4.83 (NFO t, 2H), 4.50 – 4.48 (NFO t, 2H), 4.25 (s, 5H), 1.98 (dd, J=1.6, 1.0, 3H). 13C NMR (101 MHz, acetone-d6) δ = 171.71, 167.40, 137.13, 126.53, 91.69, 72.37, 71.78, 70.95, 70.61, 65.82, 65.76, 18.49. IR 1713 cm-1 (C=O), 2022 cm-1, 2053 cm-1, 2096 cm-1 (CoC≡O)  Synthesis of polymer 3.4  Complex 3.2 (0.4630 g, 0.71 mmol) and 0.0181 g (0.11 mmol) of AIBN and 2 mL of DMF were stirred for 18 hours at 70 oC. The contents of the reaction flask were then added to 100 mL of methanol and placed in the freezer. The precipitate was then collected and washed further with methanol to remove the lower molecular weight monomers and polymers  120  1H NMR (400 MHz, CDCl3) δ = 4.85 (br. s, 4H), 4.65 (br. s, 2H), 4.42 (br. s, 2H), 4.22 (br. s, 5H), 1.84 (br. s, 2H), 1.60 (br. s, 2H), 1.07 (br. s, 1H), 0.93 (br. s, 1H). IR 1714  (C=O)   Synthesis of polymer 3.5  Under nitrogen, polymer 3.4 (0.0712 g) was dissolved in 30 mL dry THF and dicobalt octacarbonyl (0.0651 g) was added. After 30 minutes of stirring carbon monoxide stopped evolving from the reaction. The reaction was concentrated to 10 mL of THF and 50 mL of acetone was added. A small amount of precipitate was filtered from the solution and the solvent was removed from the filtrate in vacuo. 1H NMR (400 MHz, CDCl3) δ = 5.35 (br. s, 2H), 5.06 (br. s, 2H), 4.83 (br. s, 2H), 4.40 (br. s, 2H), 4.20 (br. s, 5H), 2.02 (br. s, 1H), 1.64 (br. s, 2H), 1.38 (br. s, 1H), 1.05 (br. s, 1H), 0.82 (br. s, 0H). IR 1712 (C=O), 2023 cm-1, 2054 cm-1,  2096 cm-1 (CoC≡O)  Synthesis of complex 3.7  Complex 2.17 (1.1887 g, 1 mmol) was dissolved in 20 mL DCM, 15 drops of pyridine and methacryloyl chloride (3.6) (0.21 mL, 2 mmol) were added. The reaction mixture was stirred for 18 hours under N2 in the dark. After 18 hours the solvent was removed in vacuo to give a yellow film. The film was dissolved in acetone and precipitated into H2O with 0.173 g NH4PF6. The light yellow precipitate was collected and allowed to dry under reduced pressure for 24 hours.  1.1551 g, (98 % yield). 121  1H NMR (400 MHz, acetone-d6) δ = 7.48 (d, J=8.8, 4H), 7.33 (d, J=8.8, 4H), 6.81 (d, J=6.4, 4H), 6.51 (d, J=6.4, 4H), 6.10 (dd, J=1.5, 1.0, 1H), 5.72 – 5.68 (m, 1H), 5.45 – 5.33 (m, 10H), 4.84 (t, J=1.8, 2H), 4.75 (t, J=1.8, 2H), 2.59 – 2.53 (m, 2H), 2.27-2.21 (m, 2H), 1.92 (dd, J=1.6, 1.0, 3H), 1.76 (s, 3H). 13C NMR (101 MHz, acetone-d6) δ = 173.00, 166.11, 152.37, 147.98, 136.89, 134.03, 130.75, 126.77, 121.41, 105.07, 88.02, 81.83, 81.73, 80.62, 77.37, 52.80, 52.58, 46.44, 37.18, 29.73, 27.94, 18.38. IR 1730 cm-1 (C=O)  Synthesis of polymer 3.8  Complex 3.7 (1.1439, 0.9 mmol) and AIBN (0.0381 g, 0.30 mmol) were dissolved in acetone (10 ml) and refluxed under N2 for 18 hours.  The reaction was then quenched in 100 mL of 1.2 M HCl containing NH4PF6 collected via filtration. The precipitate was triturated in DCM to remove unreacted monomer. The residual polymer was redissolved in acetone and precipitated into ether, giving 0.9926 g of polymer. 1H NMR (400 MHz, acetone-d6) δ = 7.47 (br. s, 4H), 7.31 (br. s, 4H), 6.75 (br. s, 4H), 6.44 (br. s, 4H), 5.33 (br. s, 10H), 4.74 (br. s, 4H), 2.54 (br. s, 3H), 2.23 (br. s, 3H), 1.73 (br. s, 4H), 1.47 – 0.79 (m, 4H). IR 1732 cm-1 broad (C=O)  Synthesis of polymer 3.9  Polymer 3.8 (0.2586 g), THF (15 mL) and 0.1330 g (0.4 mmol) Co2(CO)8 (2.10) were combined in an inert atmosphere chamber. To the rapidly stirring solution 1 mL of DMF was 122  added to dissolve the polymer and rapid evolution of gas occurred, the reaction mixture was stirred for 18 hours under N2. The THF was removed in vaco and the residual reaction mixture precipitated into ether. The precipitated was collected and dissolved into acetone to facilitate the removal of unwanted cobalt carbonyl by products. The solution was filtered through celite several times to remove the unwanted precipitated. The acetone was removed en vacuo to yield 0.2519 g of the pure polymer. 1H NMR (400 MHz, acetone-d6) δ = 7.47 (bs, 4H), 7.32 (bs, 4H), 6.82 (m, 4H), 6.51 (m, 4H), 5.37 (m, 12H), 4.74 (s, 2H), 2.56 (s, 3H), 2.25 (s, 3H), 1.75 (bs, 4H), 1.50 – 0.79 (m, 3H). IR 2098 cm-1, 2057 cm-1, 2026 cm-1 (C≡O), 1737 cm-1 (C=O)  Synthesis of complex 3.10  Complex 2.23 (1.08 g, 2 mmol) was dissolved in 20 mL DCM, 15 drops of pyridine and methacryloyl chloride (0.37 mL, 4 mmol) (3.6) were added. The reaction mixture was stirred for 18 hours under N2 in the dark. After 18 hours the solvent was removed in vacuo to give a yellow film. The film was dissolved in acetone and precipitated into H2O with NH4PF6. The light yellow precipitate was collected and allowed to dry under reduced pressure for 24 hours. The yield was 1.0761 g (83 % yield). 1H NMR (400 MHz, acetone-d6) δ = 8.17 (d, J=8.7, 2H), 7.48 (d, J=8.7, 2H), 6.87 (d, J=6.8, 2H), 6.66 (d, J=6.8, 2H), 6.11 (s, 1H), 5.75 – 5.68 (m, 1H), 5.42 (s, 5H), 5.06 (t, J=1.7, 2H), 4.88 (t, J=1.6, 2H), 1.96 – 1.90 (m, 3H). 13C NMR (101 MHz, acetone-d6) δ = 166.04, 165.18, 158.73, 136.87, 133.33, 132.47, 132.12, 130.96, 129.39, 128.41, 126.74, 121.35, 105.61, 88.19, 82.16, 81.53, 80.92, 78.79, 53.41, 52.79, 18.39. DCU at 31.98, 30.76, 26.12, 25.42, 25.20, 24.69. 123  IR 1735 cm-1, 1730 cm-1 (C=O)  Synthesis of polymer 3.11  Complex 3.10 (0.4244 g, 0.6 mmol) and AIBN ( 0.0277 g, 0.2 mmol) were dissolved in acetone (5 ml) and refluxed under N2 for 18 hours.  The reaction was then quenched in 100 mL of 1.2 M HCl containing NH4PF6 collected via filtration. The precipitate was triturated in DCM to remove unreacted monomer and low molecular weight oligomers. The residual polymer was re-dissolved in acetone and precipitated into ether. Yielding 0.4114 g of polymer. 1H NMR (400 MHz, acetone-d6) δ = 8.15 (br. s, 1H), 7.44 (br. s, 1H), 6.82 (br. s, 1H), 6.59 (br. s, 1H), 5.38 (br. s, 3H), 5.04 (br. s, 1H), 4.79 (br. s, 1H), 3.39 (br. s, 2H), 2.09 (br. s, 5H), 1.09 (br. s, 4H). IR 1737 cm-1 (C=O)  Synthesis of polymer 3.12 Polymer 3.11 (0.0498 g, 0.07 mmol), THF (15 mL) and Co2(CO)8 ( 2.10) (0.0535 g, 0.16 mmol) were combined in an inert atmosphere chamber. To the rapidly stirring solution 1 mL of DMF was added to dissolve the polymer and rapid evolution of gas occurred, the reaction mixture was stirred for 18 hours under N2. The THF was removed in vaco and the residual reaction mixture precipitated into ether. The precipitated was collected and dissolved into acetone to facilitate the removal of an unwanted precipitate. The solution was filtered through celite several times to remove the precipitate and acetone was removed in vacuo to yield 0.0273 g of the polymer. IR 1720 cm-1 (C=O), 2103 cm-1, 2063 cm-1, 2032 cm-1 (CoC≡O) 124    Pyrolysis of complexes 3.8 and 3.11  Polymers 3.8 and 3.11 were individually placed in a pyrolysis chamber at 200 oC under vacuum for 30 min. The polymers were then triturated with water, filtered and allowed to dry for 24 hours over vacuum. Preparation for GPC involved dissolving the polymers in THF and filtering through a 45 micron nylon filter, before injection onto the column.  125  Chapter 4:   Condensation polymers 4.1  Introduction Condensation polymerization is a powerful tool that can attach monomers together via a condensation reaction.  Perhaps the most well known condensation polymerization is that between adipic acid and 1,6-hexanediamine that produces nylon-6,6.  As was discussed in chapter 1, η6-halo-arene-η5-cyclopentadienyliron(II) hexafluorophosphate salts are highly susceptible to nucleophilic aromatic substitution to form ethers, thioethers and di-substituted amines.12, 17, 18, 21, 21  This high susceptibility to nucleophilic aromatic substitution means that the incorporation of η6-halo-arene-η5-cyclopentadienyliron(II) hexafluorophosphate salts into various monomers can allow for the formation of a large number of condensation  polymers.12, 20, 48, 71  Work performed by previous members of the Abd-El-Aziz group has shown that there are two main strategies that use η6-arene-η5-cyclopentadienyliron(II) hexafluorophosphate salts to afford condensation polymers.12, 20, 48, 71-74  The first strategy uses various aliphatic and aromatic dithiols, as well as, aromatic diol complexes that are reacted with η6-p-dichlorobenzene-η5-cyclopentadienyliron(II) hexafluorophosphate to afford various polymers of the form in Figure 4.1.  The second strategy requires the synthesis of molecules with two terminal η6-chloro-arene-η5-cyclopentadienyliron(II) hexafluorophosphate salts which could then be reacted with various dithiols, diamines, or diphenols to give polymers of the form in Figure 4.2.12, 48, 75  Figures 4.1 and 4.2 show that many different polymers can be synthesized and numerous moieties can be incorporated, with azo dyes and ferrocene providing only two of the possible examples. 126   Figure 4.1: Previously reported condensation polymers of η6-arene-η5-cyclopentadienyliron(II) hexafluorophosphate salts. 127   Figure 4.2: Previously reported condensation polymers of η6-arene-η5-cyclopentadienyliron(II) hexafluorophosphate salts.  In this chapter, monomers containing alkyne groups or alkyne coordinated dicobalt hexacarbonyl moieties with two terminal η6-chloro-arene-η5-cyclopentadienyliron(II) 128  hexafluorophosphate salts will be reacted with dithiols and bisphenol A to give condensation polymers via the second strategy.   4.2 Synthesis and characterization of condensation polymers containing η6-arene-η5-cyclopentadienyliron(II) and cobalt carbonyl 4.2.1 Synthesis of a monomer containing η6-arene-η5-cyclopentadienyliron(II) and alkyne moieties  An alkyne-containing complex with two terminal η6-chloro-arene-η5-cyclopentadienyliron(II) hexafluorophosphate salts (4.1) was prepared through the reaction of  2-butyne-1,4-diol (2.5) with two equivalents of complex 2.22 (Scheme 4.1).  This complex is quite similar to that of 2.23 where only one of the alcohols of the 2-butyne-1,4-diol were reacted.   Scheme 4.1: Synthesis of complex 4.1. 129   The 1H NMR spectrum for complex 4.1 shows all of the expected resonances and confirms that the 2-butyne-1,4-diol has been reacted through both alcohols (Figure 4.3).  Identification of the methylene resonances for these two complexes are very similar and spectrally the main differences between these complexes is that for 4.1 the methylenes appear as a singlet at 5.11 ppm rather then two sets of triplets at 5.01 and 4.26 ppm.  The non-complexed arene hydrogens resonate as doublets at 8.12 and 7.45 ppm, while the complexed arene hydrogens resonate as doublets at 6.85 and 6.57 ppm.  The cyclopentadienyliron hydrogens resonate as a sharp singlet at 5.30 ppm.   Figure 4.3: 1H NMR spectrum of complex 4.1 in DMSO-d6.  The 13C NMR spectrum for complex 4.1 contains all of the expected peaks (Figure 4.4).  This spectrum is also very similar to that of complex 2.17, with a similar pattern of peaks.  The 130  resonance for the carbonyl carbon appears at 164.17 ppm.  The non-complexed arenes have resonances at 157.65, 132.16, 130.44 and 120.37.  While the complexed arene has resonances at 126.44, 104.11, 86.92 and 77.75 ppm.  The complexed cyclopentadiene appears at 79.58 ppm and the alkyne carbons resonate at 81.34 ppm.  The methylenes were found at 52.70 ppm.  There is also a small amount of DCU and DCC present in the sample, 154.13, 135.50, 53.60, 49.01, 31.28, 30.31, 25.51, 25.10, 24.93 and 24.07 ppm. The typical process used for the removal of DCU involves dissolving the sample in small amounts of acetone or DCM, followed by cooling to -10 oC for 2 hours followed by filtering out any DCU crystals formed.  Unfortunately complex 4.1 was not as soluble in acetone or DCM as previous complexes making it necessary to use slightly more solvent and resulting in the retention of a small amount of impurities.  Figure 4.4: APT 13C NMR spectrum of complex 4.1 in DMSO-d6. 131  4.2.2 Condensation polymerization of a monomer containing η6-arene-η5-cyclopentadienyliron(II) and alkyne moieties with dithiol linkers  Condensation of complex 4.1 with various dithiols 4.2 a-c produced polymers 4.3 a-c (Scheme 4.2).  These polymers showed a significant change in solubility compared to the monomers.  While the monomers had been soluble in DCM, acetone, DMSO, and acetonitrile, the polymers would not dissolve in these solvents.  Due to these insolubility issues no NMR spectral analysis or molecular weight determination could be done on polymers 4.3 a-c.  Scheme 4.2: Synthesis of polymers 4.3 a-c.  132  4.2.3 Coordination of cobalt carbonyl to a monomer containing η6-arene-η5-cyclopentadienyliron(II) and alkyne moieties   Dicobalt octacarbonyl was coordinated to the alkyne of complex 4.1 to give monomer 4.4 which contained η6-arene-η5-cyclopentadienyliron(II) and dicobalt hexacarbonyl alkyne moieties (Scheme 4.3).  The complexes were isolated as red solids and characterized through NMR and IR spectroscopies.   Scheme 4.3: Synthesis of complex 4.4.  1H NMR spectrum of complex 4.4 shows the inclusion of the cobalt carbonyl with the downfield shift of the methylene protons to 5.67 ppm (Figure 4.5). The 13C NMR spectrum also confirms the full inclusion of the cobalt carbonyl with the shift of the methylene resonance to 55.7 ppm and the shift of the alkyne carbon resonance to 90.1 ppm (Figure 4.6). There is also the 133  appearance of a resonance at 200 ppm due to the Co-CO carbons. Neither of the NMR spectra for this compound are pure, both contain the DCU and DCC peaks that were present in the starting material as well as a very small amount of material that did not have complex 2.22 attached to both sides of the 2-butyne-1,4-diol (2.5).    Figure 4.5: 1H NMR of complex 4.4 in DMSO-d6. Fe+PF6-OClOOOOOClFe+PF6-CoCoOC COOCCOCOOC134    Figure 4.6: APT 13C NMR spectrum of complex 4.4 in DMSO-d6.  The IR of complex 4.4 shows the appearance of the three characteristic cobalt carbonyl bands at 2097, 2057 and 2037 cm-1.  4.2.4 Condensation polymerization of a monomer containing η6-arene-η5-cyclopentadienyliron(II) and dicobalt hexacarbonyl moieties with dithiol linkers Polymerization of complex 4.4 was attempted using the same linking dinucleophiles as used for the cobalt free complex 4.1 (Scheme 4.4). The polymers produced from reactions with dithiol linkers were not as expected; these insoluble polymers were yellow in appearance and Fe+PF6-OClOOOOOClFe+PF6-CoCoOC COOCCOCOOC135  lacked the three characteristic IR cobalt carbonyl bands, indicating the decomposition of the alkyne cobalt carbonyl complex. Studies on similar compounds are currently underway to determine if the decomposition of the alkyne cobalt carbonyl complex results in the restoration of the triple bond.  Scheme 4.4: Synthesis of polymers 4.5 a-c.  4.3 Thermal analysis of polymers The polymers were analyzed by both DSC and TGA to determine their thermal properties. All of the polymers were stable up to approximately 200 °C where the cationic cyclopentadienyliron complex decomposed. This decomposition, while significant, is not truly representative of the polymer degradation since the cationic cyclopentadienyliron moieties are pendent to the backbone of the polymer.  The polymer backbones of the polymers did not begin to degrade until approximately 400 °C. The TGA data is tabulated in Table 4.1.  136  Table 4.1: Thermogravimetric analysis of polymers. Polymer Step 1 Step 2 Step 3 Step 4 4.3 a 237 – 279, 17% 372 – 423, 37% 875 – 1000, 10%  4.3 b 202 – 240, 18%  386 – 429, 33% 500 – 1000, 15%  4.3 c 216 – 232, 13% 438 – 492, 22% 512 – 1000, 20%  4.5 a 209 – 259, 15% 381 - 431, 21% 570 – 623, 14% 695 – 1000, 12% 4.5 b 163 – 174, 3% 204 – 227, 10% 396 – 495, 56%  4.5 c 214 – 254, 16% 421 – 516, 16% 750 – 987, 23%   DSC showed that the polymers displayed reproducible glass transition temperatures between 100 °C and 130 °C (Table 4.2). As glass transitions are exclusive to polymers and large oligomers, the presence of these phase transitions indicates that the polymerization reactions did work.  Table 4.2: Differential scanning calorimetry of polymers.  Polymer Tg (oC) 4.3 a 125 4.3 b 107 4.3 c 107 4.5 a 123 4.5 b 101 4.5 c 130  137  4.4 Cyclic voltammetry of complexes The electrochemical properties of complexes 4.1 and 4.4 were studied using cyclic voltammetry. The complexes showed behaviour similar to those described previously. Complex 4.1 showed a reversible redox couple at E1/2 = -1.42 V due to the reversible reduction of cationic cyclopentadienyliron moiety. Complex 4.4 displayed two electrochemical processes, the first, a irreversible reduction at -1.25 V due to the cobalt centres and a reversible reduction at E1/2 = -1.44 V.  Table 4.3: Cyclic voltammetry of monomers. Complex  E1/2  Ep,c 4.1 -1.42  4.4 -1.44 -1.25  4.5 Summary This project developed the synthetic methodology to prepare an alkyne containing organoiron complex where the alkyne moiety is sandwhiched between two η6-chloroarene-η5-cyclopentadienyliron(II) moieties. The terminal chloro groups on the cyclopentadienyliron complexes allowed for polycondensation with a number of dithiols which gave highly insoluble materials. The materials showed glass transition temperatures from 100 oC - 130 oC and thermal gravimeteric analysis showed the the polymers were thermally stable up to ~200 oC where the cationic cyclopentadienyliron moieties decomposed.  The organoiron alkyne complex reacted with dicobalt octacarbonyl to generate a tetrametallic species containing both iron and cobalt. This complex was also reacted with dithiols in the presence of K2CO3 to generate insoluble 138  materials. IR analysis showed that the polymerization conditions led to the decomposition of the alkyne-hexacarbonyldicobalt moiety.  4.6  Detailed experimental All reactions and complexes containing a η6-aryl- η5-cyclopentadienyl iron hexafluorophosphate moiety were kept in the dark to prevent decomposition.  Synthesis of complex 4.1  Complex 2.22 (4.3529 g, 8.5 mmol), 2-butyne-1,4-diol (2.5) (0.2841 g, 3.5 mmol), DCC (1.8540 g, 9 mmol), DMAP (1.1432, 9 mmol), 15 mL DCM and 5 mL DMF were stirred for 18 hours, in the dark, under nitrogen.  The reaction was then placed in the freezer for 3 h and filtered to remove DCU. DCM (50 mL) was added to the filtrate which was then washed twice with 200 mL of 1.2 M HCl and 4 mmol of NH4PF6.  The organic layer was dried using magnesium sulphate followed by gravity filtration.  The DCM was removed from the filtrate using a rotary evaporator, leaving a mixture of product and DCU in DMF.  This mixture was placed in the freezer for 3 hours, resulting in the precipitation of DCU crystals which were then filtered out.  The filtrate was then added to 200 mL of water and 4 mmol of NH4PF6 forming a yellow precipitate, which was collected in a Buchner funnel and dried over vacuum.  In cases where there was still DCU in the product, the product was dissolved in a minimal amount of DCM and placed in the freezer until the DCU crystallized.  The DCU crystals were then filtered out of the solution and the DCM was removed in vacuo. 3.097 g (82 % yield). 1H NMR (400 MHz, DMSO-d6) δ = 8.12 (d, J=8.9, 4H), 7.45 (d, J=8.9, 4H), 6.85 (d, J=6.9, 4H), 6.57 (d, J=6.9, 4H), 5.30 (s, 10H), 5.11 (s, 4H).  1H NMR (400 MHz, acetone-d6) δ = 8.19 (d, 139  J=8.7, 4H), 7.49 (d, J=8.7, 4H), 6.89 (d, J=7.0, 4H), 6.67 (d, J=7.0, 4H), 5.44 (s, 5H), 5.10 (s, 4H). 13C NMR (101 MHz, DMSO-d6) δ = 164.17, 157.65, 132.16, 130.44, 126.44, 120.37, 104.11, 86.92, 81.34, 79.58, 77.75, 52.70.  DCU and DCC = 154.13, 135.50, 53.60, 49.01, 31.28, 30.31, 25.51, 25.10, 24.93, 24.07. IR 1727 cm-1 (C=O)  Synthesis of polymers 4.3 a-d  Complex 4.1 (0.2 mmol), the appropriate linker 4.2 a-d (0.2 mmol), and K2CO3 (5 mmol) were stirred in 2 mL of DMF, under N2, at 55 oC until they became viscous, typically 48-72 hours.  The reaction was then dissolved in an additional 5 mL of DMF and slowly added to H2O (200 mL) and NH4PF6 (0.4 mmol) forming a precipitate that was collected by filtration and washed with 20 mL of water. 4.3 a 0.1987 g, IR 1721 cm-1 (C=O) 4.3 b 0.2191 g, IR 1718 cm-1 (C=O) 4.3 c 0.2245 g, IR 1737 cm-1 (C=O)  Synthesis of complex 4.4  In a N2 environment, 2.1589 g (2 mmol) of complex 4.1 and 1.0382 g (3 mmol) of Co2CO8 were stirred in 10 mL of dry THF for 10 hours, for the first half hour gas was evolved from the reaction.  The THF was removed in vacuo and the complex was dissolved in acetone. After 20 min a precipitate was formed and filtered out.  The filtrate was then slowly added to 140  100 mL of water and 4 mmol of NH4PF6, forming a precipitate which was collected.  Once the product was dry it appeared as a red solid with 2.5934 g yield (95 % yield). 1H NMR (400 MHz, DMSO-d6) δ = 8.15 (d, J=8.7, 4H), 7.44 (d, J=8.7, 4H), 6.86 (d, J=6.8, 4H), 6.60 (d, J=6.8, 4H), 5.67 (s, 4H), 5.30 (d, J=10.6, 10H), 2.08 (s, 3H). 13C NMR (101 MHz, DMSO-d6) δ = 198.92, 164.71, 157.87, 131.87, 130.06, 126.53, 119.87, 104.15, 90.12, 86.96, 79.58, 78.18, 55.77.  DCC and DCU = 154.08, 135.47, 53.55, 48.95, 31.24, 30.27, 25.47, 25.06, 24.89, 24.03. IR 2097 cm-1, 2057 cm-1, 2037 cm-1 (C≡O), 1716 cm-1 (C=O)  Synthesis of polymers 4.5 a-c  0.05 mmol of complex 4.4, 0.05 mmol of the appropriate linker 4.2 a-d, and 5 mmol of K2CO3 were stirred in 1 mL of DMF, under N2, at 55-60 oC until they became viscous 48-72 hours.  Once the reaction became viscous it was dissolved in an additional 5 mL of DMF and slowly added to 200 mL of H2O and 1 mmol of NH4PF6, forming a precipitate that was collected by filtration and washed with 20 mL of water. 4.5 a 0.0678 g yield, IR 1741 cm-1 (C=O) 4.5 b 0.0567 g yield, IR 1728 cm-1 (C=O) 4.5 c 0.0501 g yield, IR 1736 cm-1 (C=O) 141  Chapter 5:  Preliminary work with polysiloxanes 5.1 Introduction Polysiloxanes, often referred to as silicones, is a class of polymeric materials well known for their their flexible backbone, thermal stability, durability, resistance to biological degradation and insulation properties.76 Due to these useful properties, polysiloxanes have found applications as lubricants, adhesives, mechanical tubing, gaskets, medical implants, medical tools and electrical insulators.  Two popular uses of polysiloxanes are in the manufacturing of contact lenses and the children’s toy Silly Putty™. Also the low carbon content of polysiloxanes has made them desirable precursors for conducting ceramic materials.   A very convenient chemical reaction for the preparation of functionalized siloxanes and polysiloxanes is hydrosilation. Hydrosilation (aka hydrosilylation) is a term that refers to the addition of an organic or inorganic silicon hydride across a double bond (Figure 5.1).  The reaction is quite versatile with respect to the X and Y substituents, which can include alkyl, aryl, alkoxy, acyloxy and halogen.  The first mention of this type of reaction was made in a patent by Miller and Schreiber in 1945.77, 78  Their method required extreme temperatures of 610-720 oC, which potentially could lead to the decomposition of starting materials. Hydrosilation catalysts are often used to alleviate the issue of starting material degradation.77  142  Y + SiXHXXCatalystYSiXXXYSiX XX Figure 5.1: Hydrosilation of a terminal alkene.  Most transition metal catalysts that have been developed to mediate hydrosilation reactions give the products according to the anti-Markovnikov rule,79  though some palladium catalysts are known to give the α-adduct of the product.  The mechanism of the catalyzed hydrosilation reaction is quite complex and can be different depending on the catalyst, reactants and experimental conditions,  meaning that the mechanism has not been elucidated for many of the reactants.80  Unfortunately, transition metal catalyzed hydrosilation is often accompanied by side reactions such as oligomerization, polymerization, isomerization hydrogenation of alkenes and dehydrogenation of silicon hydrides.79  This chapter details the synthesis of three polysiloxanes which contain η6-aryl-η5cyclopentadienyliron(II) hexafluorophosphate moieties.  This project lays the foundation for future work within the Abd-El-Aziz group with polysiloxanes and the incorporation of transition metals.     143  5.2 Synthesis and characterization of polysiloxanes containing η6-arene-η5-cyclopentadienyliron 5.2.1 glyph1197ucleophilic substitution of η6-halo-arene-η5-cyclopentadienyliron with allylamine  Complexes 5.2 a-c were synthesized via nucleophilic aromatic substitution of three different η6-chlorobenzene-η5cyclopentadienyliron(II) hexafluorophosphate complexes (2.14 a-c) with allylamine (5.1)(Scheme 5.1).  All three complexes appeared red in colour as has been seen previously for complexed anilines.81  All three complexes were highly soluble in ether, acetone, THF, DCM, DMF and DMSO.  Scheme 5.1: Synthesis of complexes 5.2 a-c.  Interestingly, even with a large excess of the amine, disubstitution of complex 2.14 a does not occur.  This has also been observed in previous attempts to prepare disubstituted amine complexes and phenylenediamine derivatives, where the formation of a zwitterion is predicted in basic solutions(Figure 5.2).81 The deprotonation of the amine results in a negative charge on the aromatic ring increasing its electron density and preventing a reaction with a second amine. 144   Figure 5.2: Deprotonation of the amine group to form a zwitterion.  The 1H NMR spectra of all three complexes are quite similar, therefore only complex 5.2 b will be explored in detail. Figure 5.3 shows the 1H NMR spectrum of 5.2 b, as can clearly be seen all of the expected resonances appear. At 6.23 ppm there is the broad singlet of the lone hydrogen on the nitrogen.  Directly upfield, at 6.17 ppm is a doublet of doublets due to two of the hydrogens of the complexed arene.  At 5.95-6.08 ppm is a multiplet that integrates for two hydrogens. This multiplet is actually the overlapping resonances of the internal allylic hydrogen and the hydrogen of the complexed arene which is para to the nitrogen.  The doublet at 5.86 is due to the final two hydrogens of the complexed arene.  At 5.40 and 5.27 ppm are two doublets of quartets due to the terminal allyl hydrogens.  At 4.99 ppm is the cyclopentadiene resonance and at 4.00 is a triplet of triplets due to the methylene.  145   Figure 5.3: 1H NMR spectrum of complex 5.2 b in acetone-d6.  The 13C NMR spectra of each complex also appear as expected, due to their similarity only the spectra for 5.2 b will be presented in detail.  Figure 5.4 shows the 13C NMR of complex 5.2 b, at 135 ppm and 118 ppm are the α and β allyl carbons respectively, while the small resonance at 127 is due to the lone quaternary carbon of the complexed arene.  The remaining resonances of the complexed arene are located at 87, 81 and 69 ppm.  The cyclopentadienyl carbons can be seen at 76 ppm and the final carbon resonance due to the CH2 is at 46 ppm.  146   Figure 5.4: APT 13C NMR spectrum of complex 5.2 b in acetone-d6.  5.2.2 Hydrosilation of allylamine complexes with methyldiethoxysilane  Hydrosilation of complexes 5.2 a-c was performed with methyldiethoxysilane using dicyclopentadienylplatinum dichloride as the catalyst in THF (Scheme 5.2).  While two different hydrosilation isomers are possible, only one product is evident in the NMR spectra.  Complexes 5.4 a-c are quite fragile as even atmospheric moisture will start to cleave the ethoxy groups from the Si. As a result, the pure compound must be under anhydrous conditions. 147   Scheme 5.2: Synthesis of complexes 5.4 a-c.  Spectroscopically all three compounds (5.4 a-c) are quite similar to each other, the only differences being due to the R group on the complexed aromatic. For this reason only 5.4 b will be described in great detail. 1H NMR of complex 5.4 b indicates the successful incorporation of the methyldiethoxysilyl moiety (Figure 5.5).  The disappearance of the allylic resonances, as well as, the lack of a Si-H peak between 4 and 5 ppm, indicates that the hydrosilation reaction went to completion.  Three peaks associated with the incorporation of the methyl diethoxy silane group are clearly seen in the spectrum, with the methyl resonance at 0.11 ppm and the ethoxy resonances at 3.77 and 1.17 ppm.  The resonances due to the internal propyl group appeared at 0.65, 1.8 and 3.3 ppm.  However, the multiplicity of these resonances was complicated by the overlapping of the major and minor product peaks.  148   Figure 5.5: 1H NMR spectrum of complex 5.4 b in acetone-d6.  The 13C NMR spectrum (Figure 5.6) of complex 5.4 b presents a slightly less complicated picture then the 1H NMR spectrum.  Each of the eleven expected carbon resonances can be seen clearly. The reaction is confirmed through the disappearance of the allylic hydrogens at 135 and 118 ppm (for complex 5.2 b) and the three internal propyl carbons of complex 5.4 b resonate at 58.68, 23.17, and 12.00 ppm. At 46.43 and 18.91 ppm are the ethoxy carbons and at -4.71 ppm is the methyl group attached to the silicon.   149   Figure 5.6: APT 13C NMR spectrum of complex 5.4 b in acetone-d6.  5.2.3 Cleavage of ethoxy groups from complexes 5.4 a-c  Cleavage of the ethoxy groups can be accomplished through the addition of water to complexes 5.4 a-c, giving the silanol adducts 5.5 a-c and ethanol (Scheme 5.3, shows the conversion of the major product only).  Attempts to isolate 5.5 a-c have so far been unsuccessful due to the polymerization of these highly reactive monomers.  However, the cleavage of the ethoxy groups can be observed using NMR spectroscopy.  Figure 5.8 shows the time lapse 1H NMR spectra of the reaction of complex 5.4 b with D2O.  The bottom spectrum is of 5.4 b prior to the addition of a drop of D2O, the other spectra in ascending order are from 1 min., 3 min., 5 150  min. and 20 min. after addition of D2O. It is important to note that the addition of D2O to the NMR tube, caused a slight shift in the 1H resonances (see Figure 5.8 before and after 1 min.). When comparing these spectra, the region from 3.5 - 4.0 ppm is particularily interesting; before any D2O was added the quartet of the ethoxy group was seen at ~3.8 ppm. One minute after addition,  a broad peak at ~3.6 ppm is observed which represents the free ethanol, at the 3 minute mark the resonance at ~3.6 ppm had intensified into a clear quartet and the peak at ~3.8 ppm had shrunk.  After 20 min. the ethoxy peaks were completely lost and the ethanol peak is the only one that appears in that region. Figure 5.8 also shows just how reactive the silanol complexes are, by 20 min. into the reaction two broadened resonances can be seen for the methyl group between 0.0 and 0.2  ppm, this is possibly due to the formation of dimers as the monomers begin to react with each other.    Scheme 5.3: Cleavage of ethoxy groups from complexes 5.4 a-c.  151   Figure 5.7: 1H NMR spectral visualization of the cleavage of the ethoxy groups from complex 5.4 b through a reaction with D2O in acetone-d6.   5.2.4 Polymerization  Due to the reactivity of the silanol groups, cleavage of the ethoxy groups and polymerization were done in a one pot process (Scheme 5.4). Water was added to solutions of the monomers to cleave off the ethoxy groups and H2SO4 was used to catalyze the polymerization. After 15 hours trimethylchloro silane was added to cap the polymer ends. The molecular weights of these polymers could not be determined as the iron free analogues were insoluble in THF. 152    Scheme 5.4: Synthesis of polymers 5.6 a-c.  The 1H NMR spectrum for polymer 5.6 b can be seen in Figure 5.. As can be seen there is a distinct broadening of the proton resonances which is characteristic of polymers. Also, it is clear upon comparison with the starting complex 5.4 b that the resonances due to the ethoxy groups at 3.77 and 1.17 ppm have disappeared. The loss of the ethoxy groups is also evident in the 13C NMR spectrum (Figure 5.) as there are no carbon resonances at either 46.43 or 18.91 ppm.  153   Figure 5.8: 1H NMR spectrum of polymer 5.6 b in acetone-d6. -0.50.00.51.01.52.02.53.03.54.04.55.05.56.0 ppm154   Figure 5.9: APT 13C NMR spectrum of polymer 5.6 b in acetone-d6.  5.3 Thermal analysis of polymers Polymers 5.6 a-c were analyzed by both DSC and TGA to determine their thermal properties. From the TGA data tabulated in Table 5.1, all of the polymers were stable up to approximately 200 °C where the cationic cyclopentadienyliron complex decomposed. This decomposition, while significant, is not truly representative of the polymer degradation since the 155  cationic cyclopentadienyliron moieties are pendent to the backbone of the polymer.  The polymer backbones of the polymers did not begin to degrade until approximately 400 °C.   Table 5.1: Thermogravimetric analysis of polymers 5.6 a-c. Polymer Step 1 (oC), % Step 2 (oC), % Step 3 (oC), % 5.6 a 199 – 245, 33% 400 – 481, 13% 500 – 1000, 10% 5.6 b 205 – 246, 32% 399 – 470, 16% 950 – 998, 13% 5.6 c 122-248, 60% 757 – 842, 30%   Differential scanning calorimetry showed that polymers 5.6 a-c displayed reproducible glass transition temperatures between 80 °C and 111 °C (Table 5.2). As glass transitions are exclusive to polymers and large oligomers, the presence of these phase transitions indicates that the polymerization reactions did work.  Table 5.2: Differential scanning calorimetry of polymers 5.6 a-c. Polymer Tg (oC) 5.6 a 95 5.6 b 111 5.6 c 80  5.4 Cyclic voltammetry of complexes Electrochemical analysis of some of the allyl and silyl containing complexes showed that the reversible reduction of the iron complexes occurred at more negative E1/2s (Table 5.3) then 156  seen in previous chapters for the oxygen substituted arene complexes. This is characteristic of cyclopentadienyliron arene complexes containing electron donating substituents.  Table 5.3: Cyclic voltammetry of complexes. Complex 1st E1/2 2nd E1/2 5.2 a -1.82 -1.96 5.2 b -1.86  5.2 c -1.86  5.4 a -1.80 -1.98 5.4 b -1.88  5.4 c -1.87   5.5 Summary   A number of new cationic organoiron complexes containing amines were prepared from the reaction of haloarene coordinated cyclopentadienyliron complexes and allyl amine. The presence of the allylic group allowed for the incorporation of methyldiethylsailne via hydrosilation using a platinum catalyst. This reaction allowed for the isolation of cationic organoiron silanes that were highly moisture sensitive. The silane complexes were converted into cationic organometallic polysiloxanes through the acid catalyzed condensation of the organometallic silanols generated in situ. The polymers possessed glass transition temperatures from 80-111 oC and were thermally stable up to 163-200 oC.    157  5.6 Detailed experimental All reactions and complexes containing a η6-aryl-η5-cyclopentadienyl iron hexafluorophosphate moiety were kept in the dark to prevent decomposition.  General procedure for the synthesis of complexes 5.2 a-c  The appropriate η6-aryl- η5-cyclopentadienyl iron hexafluorophosphate (5.0 mmol) complex (2.14 a-c) was stirred under nitrogen with allylamine (14 mmol) and K2CO3 (14 mmol) in DMSO (15 mL) for 5-18 hours.  The reaction was then quenched in a 1.2 M HCl solution and the product was extracted with DCM.  The DCM/product mixture was washed twice with 150 mL of water and dried with MgSO4.  After filtering out the MgSO4, the DCM was removed from the pure product in vacuo.  5.2 a: 1.43 g, red oil (66 % yield). 1H NMR (400 MHz, acetone-d6) δ = 6.51 (d, J=7.0, 2H), 6.38 (s, 1H), 6.05 – 5.93 (m, 1H), 5.91 (d, J=7.0, 2H), 5.39 (dq, J=17.2, 1.6, 1H), 5.30 – 5.25 (m, 1H), 5.08 (s, 5H), 3.98 (tt, J=5.6, 1.5, 2H).   13C NMR (101 MHz, acetone-d6) δ = 134.83, 127.36, 118.41, 102.29, 87.35, 79.21, 68.15, 46.52. IR 3418 cm-1 (N-H) 5.2 b: 1.49 g, red oil (75% yield).  1H NMR (400 MHz, acetone-d6) δ = 6.23 (s, 1H), 6.17 (dd,  J=6.9, 5.7, 2H), 6.08 – 5.95 (m, 2H), 5.86 (d, J=6.8, 2H), 5.40 (dq, J=17.2, 1.7, 1H), 5.27 (dq, J=10.3, 1.5, 1H), 4.99 (s, 5H), 4.00 (tt, J=5.6, 1.6, 2H). 13C NMR (101 MHz, acetone-d6) δ = 134.92, 127.17, 117.70, 86.72, 81.45, 76.38, 69.05, 45.97. IR 3421 cm-1 (N-H) 158  5.2 c: 1.88 g, red oil (91 % yield). 1H NMR (400 MHz, acetone-d6) δ = 6.11 (s, 1H), 6.08 (d, J=6.9, 2H), 6.05 – 5.94 (m, 1H), 5.78 (d, J=6.9, 2H), 5.38 (dq, J=17.2, 1.7, 1H), 5.25 (dq, J=10.3, 1.5, 1H), 4.94 (s, 5H), 3.96 (tt, J=5.6, 1.6, 2H), 2.40 (s, 3H).   13C NMR (101 MHz, acetone-d6) δ = 135.40, 126.45, 118.01, 97.15, 87.37, 77.32, 68.81, 46.50, 20.18. IR 3409 cm-1 (N-H)  General hydrosilation procedures used to produce complexes 5.4 a-c  The appropriate precursor complex (5.2 a, b or c) (4 mmol), methyldiethoxysilane (8mmol) and 3 mg of dicyclopentadienylplatinum dichloride were stirred under nitrogen in dry THF (50 mL) at 55-60 oC for 20 hours.  The THF and excess methyldiethoxysilane were removed in vacuo.  The residual red oil was then dissolved in acetone and poured into 300 mL of diethyl ether forming a red oil which was then isolated.  5.4 a: 2.11 g (93 % yield). 1H NMR (400 MHz, acetone-d6) δ = 6.50 (d, J=6.7, 2H), 6.24 (s, 1H), 5.89 (d, J=6.8, 2H), 5.08 (s, 5H), 3.77 (q, J=7.0, 4H), 3.38 – 3.25 (m, 2H), 1.82-1.65 (m, 2H), 1.17 (t, J=7.0, 6H), 1.00 (t, J=7.4, 1H), 0.75-0.65 (m, 2H), 0.10 – 0.05 (m, 3H). 13C NMR (101 MHz, acetone-d6) δ = 128.03, 102.41, 87.93, 80.12, 68.91, 59.08, 47.02, 23.19, 18.93, 12.01, -4.75. IR 3408 cm-1 (N-H) 5.4 b: 2.09 (98 % yield). 159  1H NMR (400 MHz, acetone-d6) δ = 6.19 (dd, J=6.9, 5.8, 2H), 6.09 (s, 1H), 6.04 (t, J=5.9, 1H), 5.84 (d, J=6.9, 2H), 4.99 (s, 5H), 3.77 (q, J=7.0, 4H), 3.37 – 3.26 (m, 2H), 1.85 – 1.68 (m, 2H), 1.17 (t, J=7.0, 6H), 1.02 (t, J=7.3, 0H), 0.77 – 0.68 (m, 2H), 0.13 – 0.07 (m, 3H). 13C NMR (101 MHz, acetone-d6) δ = 127.77, 86.78, 81.28, 76.30, 68.42, 58.68, 46.43, 23.17, 18.91, 12.00, -4.71.  IR 3409 cm-1 (N-H) 5.4 c: 2.08 g (95 % yield). 1H NMR (400 MHz, acetone-d6) δ = 6.06 (d, J=6.8, 2H), 5.92 (s, 1H), 5.75 (d, J=6.8, 2H), 4.92 (s, 5H), 3.77 (q, J=7.0, 4H), 3.33 – 3.22 (m, 2H), 2.40 (s, 3H), 1.82 – 1.66 (m, 2H), 1.17 (t, J=7.0, 4H), 1.00 (t, J=7.4, 0H), 0.75 – 0.67 (m, 2H), 0.11 – 0.08 (m, 3H).  13C NMR (101 MHz, acetone-d6) δ = 126.61, 96.54, 87.01, 76.82, 67.75, 58.66, 46.55, 23.16, 19.81, 18.90, 11.97, -4.68. IR 3410 cm-1 (N-H)  General polymerization procedures to produce polymers 5.6 a-c  Complexes 5.4 a-c were individually dissolved in 4 mL NMP and .5 mL of water was added, these solutions were allowed to stir for 20 min.  The ethanol and excess water were then distilled off of the reactions.  Three drops of concentrated sulphuric acid was added and the reactions were stirred at 50 oC under reduced pressure for 48 hours.  Trimethylchlorosilane dissolved in 10 mL of THF was then added to the reactions and was allowed to stir for three hours. 160  5.6 a: 1H NMR (400 MHz, acetone-d6) δ = 6.45 (br. s, 2H), 5.85 (br. s, 2H), 5.00 (s, 5H), 3.28 (br. s, 2H), 1.79 (br. s, 2H), 0.67 (br. s, 2H), 0.05 (br. s, 5H).  Not soluble enough for a 13C NMR spectrum. IR 3412 cm-1 (N-H) 5.6 b: 1H NMR (400 MHz, acetone-d6) δ =  6.11 (br. s, 2H), 6.00 (br. s, 1H), 5.78 (br. s, 2H), 4.94 (br. s, 5H), 3.30 (br. s, 2H), 1.78 (br. s, 2H), 0.74 (br. s, 2H), 0.18 (br. s, 4H). 13C NMR (101 MHz, acetone-d6) δ = 127.49, 86.81, 81.44, 76.36, 68.67, 46.59, 23.22, 15.43, 14.91, -0.22. IR 3407 cm-1 (N-H) 5.6 c: 1H NMR (400 MHz, acetone-d6) δ = 6.04 (br. s, 2H), 5.79 (br. s, 2H), 4.92 (br. s, 5H), 3.35 (br. s, 2H), 2.39 (br. S, 3H), 1.84 (br. s, 2H), 0.81 (br. s, 2H), 0.21 (br. s, 4H). 13C NMR (101 MHz, acetone-d6) δ = 125.67, 95.86, 86.28, 76.10, 67.16, 45.93, 22.67, 19.11, 14.27, 1.35, -0.97. IR 3406 cm-1 (N-H)  General demetallation procedures to produce analogues of the polymers 5.6 a-c  Polymers 5.6 a-c (0.1-0.2 g) were placed in a pyrolysis chamber under vacuum at 250 oC for twenty minutes.  The organic analogues of polymers 5.6 a-c were found to be insoluble in THF, which prevent molecular weight determination.    161  Chapter 6:  General conclusions The synthetic methodology for the incorporation of organoiron and organocobalt into polymers was explored.  Three different polynorbornene and three different polymethacrylate based polymers which contained alkyne-hexacarbonyldicobalt and either η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate or ferrocene moieties were synthesized and characterized.  Norbornene monomers which contained organoiron and organocobalt were successfully polymerized using ring opening metathesis polymerization.  The soluble portions of the polynorbornene based polymers possessed molecular weights ranging from 49 500 - 55 300 and PDIs of 1.2-1.9 (estimated from the GPC analysis of their cationic iron free analogues).  Radical polymerization of methacrylate monomers which contained η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate moieties as well as alkyne functional groups, allowed for the coordination of dicobalt hexacarbonyl post polymerization.  The soluble portions of the polymethacrylate polymers which contained organoiron possessed weight averaged molecular weights ranging from 3 244 – 19 100 and PDIs of 1.1 - 1.4 (estimated from GPC analysis of the cationic iron analogues).  Thermal analysis of the polynorbornene and the polymethacrylate based polymers was quite interesting.  Thermal gravimetric analysis indicated the the carbonyl groups of the alkyne-hexacarbonyldicobalt moieties were driven from the polymers at 130-220 oC.  While the cationic cyclopentadiene groups degraded at 200-250 oC.  Through differential scanning calorimetry the glass transition temperatures of polynorbornenes containing alkyne-hexacarbonyldicobalt either could not be determined or were around 62 oC; however, once the carbon monoxide had been thermally freed from the polymers, the glass transition temperatures ranged from 82 – 92 oC.  Prior to addition of cobalt carbonyl the poly methacrylates, displayed glass transition 162  temperatures between 78 and 130 °C.  Once cobalt carbonyl was added to these polymers, no glass transition temperatures could be found until after the carbonyl groups had been thermally driven off; however, once this occurred, the glass transitions ranged from 92 – 138 °C. In chapter 4, a monomer containing η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate moieties as well as alkyne functional groups was polymerized using various dithiol linking groups.  These polymers were too insoluble to add cobalt post polymerization and their molecular weights could not be determined.  A monomer which contained both η6-(haloarene)-η5-cyclopentadienyliron(II) hexafluorophosphate and alkyne-hexacarbonyldicobalt moieties was also combined with various dithiol linking groups.  IR spectral analysis of these polymers indicated a complete loss of the CoC≡O bands, indicating that the condensation polymerization conditions are not compatible with alkyne-hexacarbonyldicobalt complexes.  Thermal gravimetric analysis of these polymers indicated that the polymers were thermally stable to 200 - 250 oC where the cationic cyclopentadienyliron moiety was cleaved.  The glass transition temperatures of these polymers ranged from 100 – 130 oC. Chapter 5 detailed the synthesis and characterization of three siloxane based polymers which contained η6-(arene)-η5-cyclopentadienyliron(II) hexafluorophosphate moieties.  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Data Reduction  Of the 21477 reflections that were collected, 3041 were unique (Rint = 0.037); equivalent reflections were merged.  Data were collected and integrated using the Bruker SAINT1 software package. The linear absorption coefficient, µ, for Mo-Kα radiation is 11.96 cm-1. Data were corrected for absorption effects using the multi-scan technique (SADABS2), with minimum and maximum transmission coefficients of 0.712 and 0.866, respectively.  The data were corrected for Lorentz and polarization effects.  Structure Solution and Refinement  The structure was solved by direct methods3.   The material crystallizes with disorder in the position of the hydroxyl group.  The disorder was modeled in two orientations. All non-hydrogen atoms were refined anisotropically.  The hydroxyl hydrogen atom was located in a 172  difference map and refined isotropically.  All C-H hydrogen atoms were placed in calculated positions but were not refined.  The final cycle of full-matrix least-squares refinement4 on F2 was based on 3041 reflections and 236 variable parameters and converged (largest parameter shift was 0.00 times its esd) with unweighted and weighted agreement factors of:  R1 = Σ ||Fo| - |Fc|| / Σ |Fo| = 0.039 wR2 = [ Σ ( w (Fo2 - Fc2)2 )/ Σ w(Fo2)2]1/2 = 0.075  The standard deviation of an observation of unit weight5 was 1.02. The weighting scheme was based on counting statistics.  The maximum and minimum peaks on the final difference Fourier map corresponded to 0.82 and –0.25 e-/Å3, respectively.   Neutral atom scattering factors were taken from Cromer and Waber6. Anomalous dispersion effects were included in Fcalc7; the values for ∆f' and ∆f" were those of Creagh and McAuley8. The values for the mass attenuation coefficients are those of Creagh and Hubbell9. All refinements were performed using the SHELXTL10 crystallographic software package of Bruker-AXS.  References  (1) SAINT. Version 7.60A. Bruker AXS Inc., Madison, Wisconsin, USA. (1997-2009).  (2) SADABS. Bruker Nonius area detector scaling and absorption correction - V2008/1, Bruker AXS Inc., Madison, Wisconsin, USA (2008). (3) SIR97 - Altomare A., Burla M.C., Camalli M., Cascarano G.L., Giacovazzo C. , Guagliardi A., Moliterni A.G.G., Polidori G.,Spagna R. (1999) J. Appl. Cryst. 32, 115-119.  (4) Least Squares function minimized: 173    Σw(Fo2-Fc2)2 (5) Standard deviation of an observation of unit weight:       [Σw(Fo2-Fc2)2/(No-Nv)]1/2     where: No  = number of observations         Nv  = number of variables  (6) Cromer, D. T. & Waber, J. T.; "International Tables for X-ray Crystallography", Vol. IV, The Kynoch Press, Birmingham, England, Table 2.2 A (1974).  (7) Ibers, J. A. & Hamilton, W. C.; Acta Crystallogr., 17, 781 (1964).  (8) Creagh, D. C. & McAuley, W.J .; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.6.8, pages 219-222 (1992).   (9) Creagh, D. C. & Hubbell, J.H..; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.4.3, pages 200-206 (1992).   (10) SHELXTL Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA. (1997).   EXPERIMEglyph817TAL DETAILS  A. Crystal Data  Empirical Formula C15H14O3Fe Formula Weight 298.11 Crystal Color, Habit red, plate Crystal Dimensions 0.12 X 0.20 X 0.45 mm Crystal System orthorhombic 174  Lattice Type primitive Lattice Parameters a = 7.3827(4) Å  b = 17.1286(8) Å  c = 19.9355(10) Å  α = 90 o  β = 90 o  γ = 90o  V = 2520.9(2) Å3 Space Group P bca (#61) Z value 8 Dcalc 1.571 g/cm3 F000 1232.00 µ(MoKα) 11.96 cm-1 B. Intensity Measurements  Diffractometer Bruker X8 APEX II Radiation MoKα (λ = 0.71073 Å)  graphite monochromated Data Images 809 exposures @ 5.0 seconds Detector Position 40.00 mm 2θmax 56.0o No. of Reflections Measured Total: 21477   Unique: 3041 (Rint = 0.037) 175  Corrections Absorption (Tmin = 0.712, Tmax= 0.866)  Lorentz-polarization C. Structure Solution and Refinement  Structure Solution Direct Methods (SIR97) Refinement Full-matrix least-squares on F2 Function Minimized Σ w (Fo2 - Fc2)2  Least Squares Weights w=1/(σ2(Fo2)+(0.0384P) 2+ 1.2522P) Anomalous Dispersion All non-hydrogen atoms No. Observations (I>0.00σ(I)) 3041 No. Variables 236 Reflection/Parameter Ratio 12.89 Residuals (refined on F2, all data): R1; wR2 0.039; 0.075 Goodness of Fit Indicator 1.02 No. Observations (I>2.00σ(I)) 2487 Residuals (refined on F): R1; wR2 0.028; 0.069 Max Shift/Error in Final Cycle 0.00 Maximum peak in Final Diff. Map 0.82 e-/Å3 Minimum peak in Final Diff. Map -0.25 e-/Å3    176            Table 2.  Atomic coordinates ( x 10^4) and equivalent isotropic          displacement parameters (A^2 x 10^3) for aa004.          U(eq) is defined as one third of the trace of the orthogonalized          Uij tensor.            ________________________________________________________________                        x             y             z           U(eq) occ          ________________________________________________________________        C(1)         4300(50)      1900(20)      1363(19)      30(5) 0.42(4)      C(2)         3380(40)      2574(17)      1562(18)      40(6) 0.42(4)      C(3)         2150(40)      2352(15)      2043(13)      35(6) 0.42(4)      C(4)         2400(30)      1540(15)      2176(14)      37(6) 0.42(4)      C(5)         3680(40)      1277(12)      1735(16)      31(5) 0.42(4)      C(1B)        4240(40)      2078(17)      1316(15)      35(4) 0.58(4)      C(2B)        3060(30)      2626(14)      1628(10)      25(2) 0.58(4)      C(3B)        2080(30)      2215(12)      2143(10)      25(2) 0.58(4)      C(4B)        2600(30)      1438(10)      2113(11)      35(4) 0.58(4)      C(5B)        3960(30)      1350(12)      1625(13)      38(5) 0.58(4)      C(6)         1107(2)       1497(1)        225(1)       21(1)      C(7)          168(3)       2184(1)        411(1)       27(1)      C(8)        -1009(2)       2007(1)        950(1)       30(1)      C(9)         -830(2)       1204(1)       1104(1)       26(1)      C(10)         489(2)        884(1)        656(1)       20(1)      C(11)        1220(2)         91(1)        695(1)       20(1)      C(12)        3508(2)       -753(1)        299(1)       23(1)      C(13)        4667(2)       -802(1)        892(1)       24(1)      C(14)        5591(2)       -838(1)       1379(1)       25(1)      O(1)          696(2)       -422(1)       1065(1)       25(1)      O(2)         2600(2)         -7(1)        262(1)       21(1)      C(15)        6713(3)       -892(1)       1987(1)       32(1) 0.703(4)      O(3)         8064(3)       -298(1)       2055(1)       34(1) 0.703(4)      C(15B)       6713(3)       -892(1)       1987(1)       32(1) 0.297(4)      O(3B)        8277(6)      -1277(3)       1835(3)       35(2) 0.297(4)      Fe(1)        1601(1)       1745(1)       1209(1)       17(1)          ________________________________________________________________    177             Table 3.  Bond lengths [A] and angles [deg] for aa004.            _____________________________________________________________               C(1)-C(5)                     1.38(3)             C(1)-C(2)                     1.39(4)             C(1)-Fe(1)                    2.03(4)             C(1)-H(1)                     0.9500             C(2)-C(3)                     1.37(3)             C(2)-Fe(1)                    2.06(3)             C(2)-H(2)                     0.9500             C(3)-C(4)                     1.43(3)             C(3)-Fe(1)                    2.00(3)             C(3)-H(3)                     0.9500             C(4)-C(5)                     1.37(3)             C(4)-Fe(1)                    2.05(3)             C(4)-H(4)                     0.9500             C(5)-Fe(1)                    2.02(3)             C(5)-H(5)                     0.9500             C(1B)-C(5B)                   1.41(3)             C(1B)-C(2B)                   1.43(3)             C(1B)-Fe(1)                   2.04(3)             C(1B)-H(1B)                   0.9500             C(2B)-C(3B)                   1.44(3)             C(2B)-Fe(1)                   2.03(2)             C(2B)-H(2B)                   0.9500             C(3B)-C(4B)                   1.39(2)             C(3B)-Fe(1)                   2.06(2)             C(3B)-H(3B)                   0.9500             C(4B)-C(5B)                   1.40(2)             C(4B)-Fe(1)                   2.02(2)             C(4B)-H(4B)                   0.9500             C(5B)-Fe(1)                   2.04(2)             C(5B)-H(5B)                   0.9500             C(6)-C(7)                     1.414(3)             C(6)-C(10)                    1.432(2)             C(6)-Fe(1)                    2.0396(17)             C(6)-H(6)                     0.9500             C(7)-C(8)                     1.415(3)             C(7)-Fe(1)                    2.0539(18)             C(7)-H(7)                     0.9500             C(8)-C(9)                     1.417(3)             C(8)-Fe(1)                    2.0446(18)             C(8)-H(8)                     0.9500             C(9)-C(10)                    1.431(2)             C(9)-Fe(1)                    2.0307(18)             C(9)-H(9)                     0.9500             C(10)-C(11)                   1.464(2)             C(10)-Fe(1)                   2.0161(17)             C(11)-O(1)                    1.209(2)             C(11)-O(2)                    1.346(2)             C(12)-O(2)                    1.446(2)             C(12)-C(13)                   1.461(3)             C(12)-H(12A)                  0.9900             C(12)-H(12B)                  0.9900             C(13)-C(14)                   1.190(3)             C(14)-C(15)                   1.470(3)             C(15)-O(3)                    1.432(3) 178              C(15)-H(15A)                  0.9900             C(15)-H(15B)                  0.9900             O(3)-H(3O)                    0.92(6)             O(3B)-H(3O2)                  0.87(10)               C(5)-C(1)-C(2)              109(3)             C(5)-C(1)-Fe(1)              69.8(19)             C(2)-C(1)-Fe(1)              71.1(18)             C(5)-C(1)-H(1)              125.5             C(2)-C(1)-H(1)              125.5             Fe(1)-C(1)-H(1)             124.8             C(3)-C(2)-C(1)              107(3)             C(3)-C(2)-Fe(1)              68.1(15)             C(1)-C(2)-Fe(1)              69.0(19)             C(3)-C(2)-H(2)              126.4             C(1)-C(2)-H(2)              126.7             Fe(1)-C(2)-H(2)             127.6             C(2)-C(3)-C(4)              108(2)             C(2)-C(3)-Fe(1)              72.4(14)             C(4)-C(3)-Fe(1)              71.0(15)             C(2)-C(3)-H(3)              125.9             C(4)-C(3)-H(3)              125.7             Fe(1)-C(3)-H(3)             122.4             C(5)-C(4)-C(3)              106.8(18)             C(5)-C(4)-Fe(1)              69.4(17)             C(3)-C(4)-Fe(1)              67.7(15)             C(5)-C(4)-H(4)              126.5             C(3)-C(4)-H(4)              126.7             Fe(1)-C(4)-H(4)             127.0             C(4)-C(5)-C(1)              109(2)             C(4)-C(5)-Fe(1)              71.4(17)             C(1)-C(5)-Fe(1)              70.5(18)             C(4)-C(5)-H(5)              125.6             C(1)-C(5)-H(5)              125.6             Fe(1)-C(5)-H(5)             125.5             C(5B)-C(1B)-C(2B)           108(2)             C(5B)-C(1B)-Fe(1)            69.9(14)             C(2B)-C(1B)-Fe(1)            69.1(14)             C(5B)-C(1B)-H(1B)           126.3             C(2B)-C(1B)-H(1B)           126.0             Fe(1)-C(1B)-H(1B)           126.4             C(1B)-C(2B)-C(3B)           107.3(19)             C(1B)-C(2B)-Fe(1)            69.9(15)             C(3B)-C(2B)-Fe(1)            70.3(12)             C(1B)-C(2B)-H(2B)           126.4             C(3B)-C(2B)-H(2B)           126.3             Fe(1)-C(2B)-H(2B)           125.2             C(4B)-C(3B)-C(2B)           107.3(16)             C(4B)-C(3B)-Fe(1)            68.5(12)             C(2B)-C(3B)-Fe(1)            68.4(11)             C(4B)-C(3B)-H(3B)           126.2             C(2B)-C(3B)-H(3B)           126.4             Fe(1)-C(3B)-H(3B)           128.2             C(3B)-C(4B)-C(5B)           109.4(14)             C(3B)-C(4B)-Fe(1)            71.6(11)             C(5B)-C(4B)-Fe(1)            70.7(12)             C(3B)-C(4B)-H(4B)           125.4 179              C(5B)-C(4B)-H(4B)           125.2             Fe(1)-C(4B)-H(4B)           124.4             C(4B)-C(5B)-C(1B)           108.3(18)             C(4B)-C(5B)-Fe(1)            68.8(12)             C(1B)-C(5B)-Fe(1)            69.8(14)             C(4B)-C(5B)-H(5B)           126.0             C(1B)-C(5B)-H(5B)           125.7             Fe(1)-C(5B)-H(5B)           126.4             C(7)-C(6)-C(10)             107.31(16)             C(7)-C(6)-Fe(1)              70.34(10)             C(10)-C(6)-Fe(1)             68.45(10)             C(7)-C(6)-H(6)              126.3             C(10)-C(6)-H(6)             126.3             Fe(1)-C(6)-H(6)             126.4             C(6)-C(7)-C(8)              108.75(16)             C(6)-C(7)-Fe(1)              69.24(10)             C(8)-C(7)-Fe(1)              69.45(11)             C(6)-C(7)-H(7)              125.6             C(8)-C(7)-H(7)              125.6             Fe(1)-C(7)-H(7)             127.3             C(7)-C(8)-C(9)              108.44(17)             C(7)-C(8)-Fe(1)              70.16(10)             C(9)-C(8)-Fe(1)              69.13(10)             C(7)-C(8)-H(8)              125.8             C(9)-C(8)-H(8)              125.8             Fe(1)-C(8)-H(8)             126.5             C(8)-C(9)-C(10)             107.41(17)             C(8)-C(9)-Fe(1)              70.19(10)             C(10)-C(9)-Fe(1)             68.75(10)             C(8)-C(9)-H(9)              126.3             C(10)-C(9)-H(9)             126.3             Fe(1)-C(9)-H(9)             126.3             C(9)-C(10)-C(6)             108.09(15)             C(9)-C(10)-C(11)            124.94(16)             C(6)-C(10)-C(11)            126.57(16)             C(9)-C(10)-Fe(1)             69.84(10)             C(6)-C(10)-Fe(1)             70.21(9)             C(11)-C(10)-Fe(1)           119.99(12)             O(1)-C(11)-O(2)             122.92(16)             O(1)-C(11)-C(10)            126.01(16)             O(2)-C(11)-C(10)            111.07(15)             O(2)-C(12)-C(13)            111.33(14)             O(2)-C(12)-H(12A)           109.4             C(13)-C(12)-H(12A)          109.4             O(2)-C(12)-H(12B)           109.4             C(13)-C(12)-H(12B)          109.4             H(12A)-C(12)-H(12B)         108.0             C(14)-C(13)-C(12)           179.1(2)             C(13)-C(14)-C(15)           179.0(2)             C(11)-O(2)-C(12)            115.29(13)             O(3)-C(15)-C(14)            115.17(17)             O(3)-C(15)-H(15A)           108.5             C(14)-C(15)-H(15A)          108.5             O(3)-C(15)-H(15B)           108.5             C(14)-C(15)-H(15B)          108.5             H(15A)-C(15)-H(15B)         107.5             C(15)-O(3)-H(3O)            109(3) 180              C(3)-Fe(1)-C(10)            156.4(8)             C(3)-Fe(1)-C(4B)             47.1(8)             C(10)-Fe(1)-C(4B)           116.5(5)             C(3)-Fe(1)-C(5)              67.7(10)             C(10)-Fe(1)-C(5)            107.6(7)             C(4B)-Fe(1)-C(5)             32.4(10)             C(3)-Fe(1)-C(9)             120.1(7)             C(10)-Fe(1)-C(9)             41.41(7)             C(4B)-Fe(1)-C(9)            107.2(5)             C(5)-Fe(1)-C(9)             122.8(7)             C(3)-Fe(1)-C(1)              66.9(12)             C(10)-Fe(1)-C(1)            125.3(10)             C(4B)-Fe(1)-C(1)             62.6(11)             C(5)-Fe(1)-C(1)              39.7(10)             C(9)-Fe(1)-C(1)             160.3(10)             C(3)-Fe(1)-C(2B)             33.5(10)             C(10)-Fe(1)-C(2B)           169.5(6)             C(4B)-Fe(1)-C(2B)            68.5(8)             C(5)-Fe(1)-C(2B)             71.4(9)             C(9)-Fe(1)-C(2B)            148.0(6)             C(1)-Fe(1)-C(2B)             47.4(11)             C(3)-Fe(1)-C(6)             160.5(8)             C(10)-Fe(1)-C(6)             41.34(7)             C(4B)-Fe(1)-C(6)            150.5(6)             C(5)-Fe(1)-C(6)             123.5(8)             C(9)-Fe(1)-C(6)              69.41(7)             C(1)-Fe(1)-C(6)             110.4(10)             C(2B)-Fe(1)-C(6)            130.1(6)             C(3)-Fe(1)-C(1B)             64.8(11)             C(10)-Fe(1)-C(1B)           130.6(8)             C(4B)-Fe(1)-C(1B)            68.2(10)             C(5)-Fe(1)-C(1B)             48.2(10)             C(9)-Fe(1)-C(1B)            169.0(8)             C(1)-Fe(1)-C(1B)              9.0(15)             C(2B)-Fe(1)-C(1B)            41.0(9)             C(6)-Fe(1)-C(1B)            109.2(8)             C(3)-Fe(1)-C(5B)             70.2(10)             C(10)-Fe(1)-C(5B)           109.0(6)             C(4B)-Fe(1)-C(5B)            40.5(7)             C(5)-Fe(1)-C(5B)              9.2(12)             C(9)-Fe(1)-C(5B)            130.0(6)             C(1)-Fe(1)-C(5B)             31.5(11)             C(2B)-Fe(1)-C(5B)            68.2(9)             C(6)-Fe(1)-C(5B)            118.3(7)             C(1B)-Fe(1)-C(5B)            40.3(7)             C(3)-Fe(1)-C(8)             106.7(7)             C(10)-Fe(1)-C(8)             68.83(7)             C(4B)-Fe(1)-C(8)            128.9(7)             C(5)-Fe(1)-C(8)             158.8(8)             C(9)-Fe(1)-C(8)              40.68(8)             C(1)-Fe(1)-C(8)             158.8(10)             C(2B)-Fe(1)-C(8)            116.0(7)             C(6)-Fe(1)-C(8)              68.53(8)             C(1B)-Fe(1)-C(8)            149.8(8)             C(5B)-Fe(1)-C(8)            168.0(7)             C(3)-Fe(1)-C(4)              41.3(9)             C(10)-Fe(1)-C(4)            120.4(7) 181              C(4B)-Fe(1)-C(4)              7.4(11)             C(5)-Fe(1)-C(4)              39.2(9)             C(9)-Fe(1)-C(4)             105.8(6)             C(1)-Fe(1)-C(4)              66.3(12)             C(2B)-Fe(1)-C(4)             65.7(9)             C(6)-Fe(1)-C(4)             157.2(8)             C(1B)-Fe(1)-C(4)             71.0(10)             C(5B)-Fe(1)-C(4)             46.8(10)             C(8)-Fe(1)-C(4)             123.2(7)            _____________________________________________________________              Symmetry transformations used to generate equivalent atoms:      182      Table 4.  Anisotropic displacement parameters (A^2 x 10^3) for aa004.     The anisotropic displacement factor exponent takes the form:     -2 pi^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]       _______________________________________________________________________                 U11        U22        U33        U23        U13        U12     _______________________________________________________________________       C(1)     11(3)      54(11)     24(9)      -6(7)      -1(5)      -6(6)     C(2)     46(13)     18(6)      56(12)      5(6)     -36(9)     -14(8)     C(3)     38(10)     37(9)      31(11)    -20(7)     -11(7)      21(7)     C(4)     24(4)      69(16)     17(4)       4(7)       4(3)      -9(7)     C(5)     27(7)      18(5)      46(11)      6(6)     -15(6)      -1(5)     C(1B)    20(5)      69(12)     18(3)       1(7)      -5(3)     -15(6)     C(2B)    21(4)      26(4)      27(3)       4(3)     -12(3)      -5(3)     C(3B)    26(4)      35(5)      12(3)      -2(3)       3(2)      -6(4)     C(4B)    61(10)     20(3)      25(6)       6(3)     -17(6)      -6(4)     C(5B)    27(6)      48(11)     38(8)     -26(6)     -20(5)      21(7)     C(6)     21(1)      22(1)      21(1)      -1(1)      -7(1)      -3(1)     C(7)     27(1)      21(1)      33(1)      -2(1)     -15(1)       1(1)     C(8)     16(1)      27(1)      48(1)     -12(1)      -9(1)       4(1)     C(9)     14(1)      27(1)      37(1)      -7(1)       2(1)      -3(1)     C(10)    15(1)      20(1)      24(1)      -3(1)      -2(1)      -3(1)     C(11)    16(1)      21(1)      21(1)      -4(1)       0(1)      -4(1)     C(12)    23(1)      18(1)      29(1)      -4(1)       3(1)       3(1)     C(13)    22(1)      18(1)      31(1)       0(1)       5(1)      -1(1)     C(14)    23(1)      20(1)      34(1)       4(1)       5(1)      -1(1)     O(1)     23(1)      21(1)      31(1)       2(1)       4(1)      -5(1)     O(2)     22(1)      18(1)      24(1)      -1(1)       4(1)       1(1)     C(15)    29(1)      33(1)      34(1)      10(1)      -2(1)      -4(1)     O(3)     36(1)      38(1)      27(1)       0(1)       0(1)      -7(1)     C(15B)   29(1)      33(1)      34(1)      10(1)      -2(1)      -4(1)     O(3B)    19(2)      46(3)      42(3)      21(2)       4(2)      -1(2)     Fe(1)    14(1)      18(1)      18(1)      -3(1)      -1(1)       0(1)     _______________________________________________________________________    183           Table 5.  Hydrogen coordinates ( x 10^4) and isotropic          displacement parameters (A^2 x 10^3) for aa004.            ________________________________________________________________                            x             y             z           U(eq)          ________________________________________________________________             H(1)         5204          1876          1025          36           H(2)         3569          3087          1397          48           H(3)         1285          2682          2252          42           H(4)         1791          1240          2508          44           H(5)         4073           752          1692          37           H(1B)        5071          2185           964          43           H(2B)        2936          3163          1517          29           H(3B)        1224          2435          2446          29           H(4B)        2121          1029          2381          42           H(5B)        4579           879          1521          45           H(6)         1985          1452          -121          26           H(7)          305          2682           207          32           H(8)        -1787          2366          1170          36           H(9)        -1468           928          1444          31           H(12A)       4252          -829          -109          28           H(12B)       2593         -1175           315          28           H(15A)       5906          -871          2383          38           H(15B)       7321         -1407          1990          38           H(15C)       6995          -363          2156          38           H(15D)       6047         -1178          2342          38           H(3O)        8900(80)      -350(30)      1720(30)      95(18)           H(3O2)       8950(110)     -960(50)      1600(40)      29(19)          ________________________________________________________________    184           Table 6.  Torsion angles [deg] for aa004.          ________________________________________________________________             C(5)-C(1)-C(2)-C(3)                                  -2(4)           Fe(1)-C(1)-C(2)-C(3)                                 57.7(19)           C(5)-C(1)-C(2)-Fe(1)                                -60(3)           C(1)-C(2)-C(3)-C(4)                                   4(3)           Fe(1)-C(2)-C(3)-C(4)                                 62.3(19)           C(1)-C(2)-C(3)-Fe(1)                                -58(2)           C(2)-C(3)-C(4)-C(5)                                  -5(3)           Fe(1)-C(3)-C(4)-C(5)                                 59(2)           C(2)-C(3)-C(4)-Fe(1)                                -63.2(19)           C(3)-C(4)-C(5)-C(1)                                   3(4)           Fe(1)-C(4)-C(5)-C(1)                                 61(2)           C(3)-C(4)-C(5)-Fe(1)                                -58(2)           C(2)-C(1)-C(5)-C(4)                                  -1(4)           Fe(1)-C(1)-C(5)-C(4)                                -61(2)           C(2)-C(1)-C(5)-Fe(1)                                 61(2)           C(5B)-C(1B)-C(2B)-C(3B)                               1(3)           Fe(1)-C(1B)-C(2B)-C(3B)                              60.7(14)           C(5B)-C(1B)-C(2B)-Fe(1)                             -59.6(18)           C(1B)-C(2B)-C(3B)-C(4B)                              -3(2)           Fe(1)-C(2B)-C(3B)-C(4B)                              57.6(15)           C(1B)-C(2B)-C(3B)-Fe(1)                             -60.4(17)           C(2B)-C(3B)-C(4B)-C(5B)                               3(2)           Fe(1)-C(3B)-C(4B)-C(5B)                              61.0(16)           C(2B)-C(3B)-C(4B)-Fe(1)                             -57.6(13)           C(3B)-C(4B)-C(5B)-C(1B)                              -3(3)           Fe(1)-C(4B)-C(5B)-C(1B)                              58.8(18)           C(3B)-C(4B)-C(5B)-Fe(1)                             -61.5(16)           C(2B)-C(1B)-C(5B)-C(4B)                               1(3)           Fe(1)-C(1B)-C(5B)-C(4B)                             -58.2(16)           C(2B)-C(1B)-C(5B)-Fe(1)                              59.1(18)           C(10)-C(6)-C(7)-C(8)                                  0.3(2)           Fe(1)-C(6)-C(7)-C(8)                                -58.34(13)           C(10)-C(6)-C(7)-Fe(1)                                58.67(11)           C(6)-C(7)-C(8)-C(9)                                  -0.5(2)           Fe(1)-C(7)-C(8)-C(9)                                -58.70(13)           C(6)-C(7)-C(8)-Fe(1)                                 58.21(12)           C(7)-C(8)-C(9)-C(10)                                  0.4(2)           Fe(1)-C(8)-C(9)-C(10)                               -58.89(12)           C(7)-C(8)-C(9)-Fe(1)                                 59.34(13)           C(8)-C(9)-C(10)-C(6)                                 -0.2(2)           Fe(1)-C(9)-C(10)-C(6)                               -60.04(12)           C(8)-C(9)-C(10)-C(11)                               172.94(16)           Fe(1)-C(9)-C(10)-C(11)                              113.14(16)           C(8)-C(9)-C(10)-Fe(1)                                59.80(12)           C(7)-C(6)-C(10)-C(9)                                 -0.06(19)           Fe(1)-C(6)-C(10)-C(9)                                59.81(12)           C(7)-C(6)-C(10)-C(11)                              -173.10(16)           Fe(1)-C(6)-C(10)-C(11)                             -113.23(17)           C(7)-C(6)-C(10)-Fe(1)                               -59.87(12)           C(9)-C(10)-C(11)-O(1)                                 7.5(3)           C(6)-C(10)-C(11)-O(1)                               179.44(17)           Fe(1)-C(10)-C(11)-O(1)                               92.81(19)           C(9)-C(10)-C(11)-O(2)                              -171.98(16)           C(6)-C(10)-C(11)-O(2)                                -0.1(2) 185            Fe(1)-C(10)-C(11)-O(2)                              -86.70(16)           O(2)-C(12)-C(13)-C(14)                               47(13)           C(12)-C(13)-C(14)-C(15)                              64(22)           O(1)-C(11)-O(2)-C(12)                                -4.1(2)           C(10)-C(11)-O(2)-C(12)                              175.39(13)           C(13)-C(12)-O(2)-C(11)                              -74.61(19)           C(13)-C(14)-C(15)-O(3)                             -168(14)           C(2)-C(3)-Fe(1)-C(10)                               163.7(17)           C(4)-C(3)-Fe(1)-C(10)                                46(2)           C(2)-C(3)-Fe(1)-C(4B)                               110.8(18)           C(4)-C(3)-Fe(1)-C(4B)                                -6.5(16)           C(2)-C(3)-Fe(1)-C(5)                                 80.7(17)           C(4)-C(3)-Fe(1)-C(5)                                -36.6(13)           C(2)-C(3)-Fe(1)-C(9)                               -163.3(14)           C(4)-C(3)-Fe(1)-C(9)                                 79.4(14)           C(2)-C(3)-Fe(1)-C(1)                                 37.4(17)           C(4)-C(3)-Fe(1)-C(1)                                -79.9(16)           C(2)-C(3)-Fe(1)-C(2B)                                -9(3)           C(4)-C(3)-Fe(1)-C(2B)                              -126(2)           C(2)-C(3)-Fe(1)-C(6)                                -48(3)           C(4)-C(3)-Fe(1)-C(6)                               -165.7(16)           C(2)-C(3)-Fe(1)-C(1B)                                27.8(16)           C(4)-C(3)-Fe(1)-C(1B)                               -89.5(15)           C(2)-C(3)-Fe(1)-C(5B)                                71.2(15)           C(4)-C(3)-Fe(1)-C(5B)                               -46.1(13)           C(2)-C(3)-Fe(1)-C(8)                               -121.1(16)           C(4)-C(3)-Fe(1)-C(8)                                121.6(12)           C(2)-C(3)-Fe(1)-C(4)                                117(2)           C(9)-C(10)-Fe(1)-C(3)                                45.5(18)           C(6)-C(10)-Fe(1)-C(3)                               164.5(18)           C(11)-C(10)-Fe(1)-C(3)                              -74.0(18)           C(9)-C(10)-Fe(1)-C(4B)                               86.3(8)           C(6)-C(10)-Fe(1)-C(4B)                             -154.8(7)           C(11)-C(10)-Fe(1)-C(4B)                             -33.3(8)           C(9)-C(10)-Fe(1)-C(5)                               120.0(9)           C(6)-C(10)-Fe(1)-C(5)                              -121.1(9)           C(11)-C(10)-Fe(1)-C(5)                                0.5(9)           C(6)-C(10)-Fe(1)-C(9)                               118.93(15)           C(11)-C(10)-Fe(1)-C(9)                             -119.51(18)           C(9)-C(10)-Fe(1)-C(1)                               160.2(13)           C(6)-C(10)-Fe(1)-C(1)                               -80.9(13)           C(11)-C(10)-Fe(1)-C(1)                               40.7(13)           C(9)-C(10)-Fe(1)-C(2B)                             -157(4)           C(6)-C(10)-Fe(1)-C(2B)                              -38(4)           C(11)-C(10)-Fe(1)-C(2B)                              83(4)           C(9)-C(10)-Fe(1)-C(6)                              -118.93(15)           C(11)-C(10)-Fe(1)-C(6)                              121.56(18)           C(9)-C(10)-Fe(1)-C(1B)                              169.5(11)           C(6)-C(10)-Fe(1)-C(1B)                              -71.6(11)           C(11)-C(10)-Fe(1)-C(1B)                              50.0(11)           C(9)-C(10)-Fe(1)-C(5B)                              129.6(8)           C(6)-C(10)-Fe(1)-C(5B)                             -111.5(8)           C(11)-C(10)-Fe(1)-C(5B)                              10.1(8)           C(9)-C(10)-Fe(1)-C(8)                               -37.79(12)           C(6)-C(10)-Fe(1)-C(8)                                81.14(12)           C(11)-C(10)-Fe(1)-C(8)                             -157.30(16)           C(9)-C(10)-Fe(1)-C(4)                                79.1(8) 186            C(6)-C(10)-Fe(1)-C(4)                              -161.9(8)           C(11)-C(10)-Fe(1)-C(4)                              -40.4(8)           C(3B)-C(4B)-Fe(1)-C(3)                                6.9(17)           C(5B)-C(4B)-Fe(1)-C(3)                             -112.2(15)           C(3B)-C(4B)-Fe(1)-C(10)                            -152.2(10)           C(5B)-C(4B)-Fe(1)-C(10)                              88.7(11)           C(3B)-C(4B)-Fe(1)-C(5)                              126.7(19)           C(5B)-C(4B)-Fe(1)-C(5)                                8(2)           C(3B)-C(4B)-Fe(1)-C(9)                             -108.5(11)           C(5B)-C(4B)-Fe(1)-C(9)                              132.4(10)           C(3B)-C(4B)-Fe(1)-C(1)                               89.8(15)           C(5B)-C(4B)-Fe(1)-C(1)                              -29.3(14)           C(3B)-C(4B)-Fe(1)-C(2B)                              37.8(10)           C(5B)-C(4B)-Fe(1)-C(2B)                             -81.3(12)           C(3B)-C(4B)-Fe(1)-C(6)                              173.0(9)           C(5B)-C(4B)-Fe(1)-C(6)                               53.9(15)           C(3B)-C(4B)-Fe(1)-C(1B)                              82.1(13)           C(5B)-C(4B)-Fe(1)-C(1B)                             -37.0(11)           C(3B)-C(4B)-Fe(1)-C(5B)                             119.1(15)           C(3B)-C(4B)-Fe(1)-C(8)                              -68.9(12)           C(5B)-C(4B)-Fe(1)-C(8)                              172.0(9)           C(3B)-C(4B)-Fe(1)-C(4)                              -28(8)           C(5B)-C(4B)-Fe(1)-C(4)                             -148(9)           C(4)-C(5)-Fe(1)-C(3)                                 38.5(13)           C(1)-C(5)-Fe(1)-C(3)                                -80.2(19)           C(4)-C(5)-Fe(1)-C(10)                              -116.9(13)           C(1)-C(5)-Fe(1)-C(10)                               124.5(18)           C(4)-C(5)-Fe(1)-C(4B)                                -4.9(19)           C(1)-C(5)-Fe(1)-C(4B)                              -124(2)           C(4)-C(5)-Fe(1)-C(9)                                -73.9(15)           C(1)-C(5)-Fe(1)-C(9)                                167.5(17)           C(4)-C(5)-Fe(1)-C(1)                                119(2)           C(4)-C(5)-Fe(1)-C(2B)                                74.1(14)           C(1)-C(5)-Fe(1)-C(2B)                               -44.6(18)           C(4)-C(5)-Fe(1)-C(6)                               -159.6(11)           C(1)-C(5)-Fe(1)-C(6)                                 81.8(19)           C(4)-C(5)-Fe(1)-C(1B)                               114.0(19)           C(1)-C(5)-Fe(1)-C(1B)                                -5(3)           C(4)-C(5)-Fe(1)-C(5B)                               143(9)           C(1)-C(5)-Fe(1)-C(5B)                                24(8)           C(4)-C(5)-Fe(1)-C(8)                                -40(3)           C(1)-C(5)-Fe(1)-C(8)                               -158.8(19)           C(1)-C(5)-Fe(1)-C(4)                               -119(2)           C(8)-C(9)-Fe(1)-C(3)                                 80.5(9)           C(10)-C(9)-Fe(1)-C(3)                              -160.7(9)           C(8)-C(9)-Fe(1)-C(10)                              -118.77(16)           C(8)-C(9)-Fe(1)-C(4B)                               130.4(7)           C(10)-C(9)-Fe(1)-C(4B)                             -110.8(7)           C(8)-C(9)-Fe(1)-C(5)                                162.0(10)           C(10)-C(9)-Fe(1)-C(5)                               -79.2(10)           C(8)-C(9)-Fe(1)-C(1)                               -174(3)           C(10)-C(9)-Fe(1)-C(1)                               -55(3)           C(8)-C(9)-Fe(1)-C(2B)                                53.7(12)           C(10)-C(9)-Fe(1)-C(2B)                              172.4(12)           C(8)-C(9)-Fe(1)-C(6)                                -80.63(13)           C(10)-C(9)-Fe(1)-C(6)                                38.14(10)           C(8)-C(9)-Fe(1)-C(1B)                              -166(4) 187            C(10)-C(9)-Fe(1)-C(1B)                              -47(4)           C(8)-C(9)-Fe(1)-C(5B)                               169.2(9)           C(10)-C(9)-Fe(1)-C(5B)                              -72.0(9)           C(10)-C(9)-Fe(1)-C(8)                               118.77(16)           C(8)-C(9)-Fe(1)-C(4)                                122.9(8)           C(10)-C(9)-Fe(1)-C(4)                              -118.4(8)           C(5)-C(1)-Fe(1)-C(3)                                 82.4(18)           C(2)-C(1)-Fe(1)-C(3)                                -37.1(17)           C(5)-C(1)-Fe(1)-C(10)                               -74(2)           C(2)-C(1)-Fe(1)-C(10)                               166.2(17)           C(5)-C(1)-Fe(1)-C(4B)                                30.2(16)           C(2)-C(1)-Fe(1)-C(4B)                               -89(2)           C(2)-C(1)-Fe(1)-C(5)                               -120(3)           C(5)-C(1)-Fe(1)-C(9)                                -33(4)           C(2)-C(1)-Fe(1)-C(9)                               -152(2)           C(5)-C(1)-Fe(1)-C(2B)                               115(2)           C(2)-C(1)-Fe(1)-C(2B)                                -4(2)           C(5)-C(1)-Fe(1)-C(6)                               -118.3(17)           C(2)-C(1)-Fe(1)-C(6)                                122(2)           C(5)-C(1)-Fe(1)-C(1B)                               157(13)           C(2)-C(1)-Fe(1)-C(1B)                                38(11)           C(5)-C(1)-Fe(1)-C(5B)                                -7(2)           C(2)-C(1)-Fe(1)-C(5B)                              -127(3)           C(5)-C(1)-Fe(1)-C(8)                                159(2)           C(2)-C(1)-Fe(1)-C(8)                                 39(4)           C(5)-C(1)-Fe(1)-C(4)                                 37.3(16)           C(2)-C(1)-Fe(1)-C(4)                                -82(2)           C(1B)-C(2B)-Fe(1)-C(3)                              124(2)           C(3B)-C(2B)-Fe(1)-C(3)                                7(2)           C(1B)-C(2B)-Fe(1)-C(10)                             -39(4)           C(3B)-C(2B)-Fe(1)-C(10)                            -157(3)           C(1B)-C(2B)-Fe(1)-C(4B)                              81.2(15)           C(3B)-C(2B)-Fe(1)-C(4B)                             -36.6(11)           C(1B)-C(2B)-Fe(1)-C(5)                               46.7(16)           C(3B)-C(2B)-Fe(1)-C(5)                              -71.1(13)           C(1B)-C(2B)-Fe(1)-C(9)                              169.4(14)           C(3B)-C(2B)-Fe(1)-C(9)                               51.6(19)           C(1B)-C(2B)-Fe(1)-C(1)                                9(2)           C(3B)-C(2B)-Fe(1)-C(1)                             -108.6(19)           C(1B)-C(2B)-Fe(1)-C(6)                              -71.8(16)           C(3B)-C(2B)-Fe(1)-C(6)                              170.4(9)           C(3B)-C(2B)-Fe(1)-C(1B)                            -117.8(18)           C(1B)-C(2B)-Fe(1)-C(5B)                              37.5(14)           C(3B)-C(2B)-Fe(1)-C(5B)                             -80.3(12)           C(1B)-C(2B)-Fe(1)-C(8)                             -154.8(13)           C(3B)-C(2B)-Fe(1)-C(8)                               87.4(12)           C(1B)-C(2B)-Fe(1)-C(4)                               88.6(16)           C(3B)-C(2B)-Fe(1)-C(4)                              -29.2(11)           C(7)-C(6)-Fe(1)-C(3)                                -42(2)           C(10)-C(6)-Fe(1)-C(3)                              -161(2)           C(7)-C(6)-Fe(1)-C(10)                               118.74(15)           C(7)-C(6)-Fe(1)-C(4B)                               169.3(11)           C(10)-C(6)-Fe(1)-C(4B)                               50.6(11)           C(7)-C(6)-Fe(1)-C(5)                               -163.0(8)           C(10)-C(6)-Fe(1)-C(5)                                78.3(8)           C(7)-C(6)-Fe(1)-C(9)                                 80.54(12)           C(10)-C(6)-Fe(1)-C(9)                               -38.20(10) 188            C(7)-C(6)-Fe(1)-C(1)                               -120.5(11)           C(10)-C(6)-Fe(1)-C(1)                               120.7(11)           C(7)-C(6)-Fe(1)-C(2B)                               -69.8(9)           C(10)-C(6)-Fe(1)-C(2B)                              171.5(9)           C(7)-C(6)-Fe(1)-C(1B)                              -111.0(8)           C(10)-C(6)-Fe(1)-C(1B)                              130.2(8)           C(7)-C(6)-Fe(1)-C(5B)                              -154.1(7)           C(10)-C(6)-Fe(1)-C(5B)                               87.1(7)           C(7)-C(6)-Fe(1)-C(8)                                 36.82(11)           C(10)-C(6)-Fe(1)-C(8)                               -81.92(11)           C(7)-C(6)-Fe(1)-C(4)                                162.4(16)           C(10)-C(6)-Fe(1)-C(4)                                43.6(16)           C(5B)-C(1B)-Fe(1)-C(3)                               88.7(16)           C(2B)-C(1B)-Fe(1)-C(3)                              -30.2(15)           C(5B)-C(1B)-Fe(1)-C(10)                             -69.7(17)           C(2B)-C(1B)-Fe(1)-C(10)                             171.3(10)           C(5B)-C(1B)-Fe(1)-C(4B)                              37.2(12)           C(2B)-C(1B)-Fe(1)-C(4B)                             -81.7(15)           C(5B)-C(1B)-Fe(1)-C(5)                                7(2)           C(2B)-C(1B)-Fe(1)-C(5)                             -112(2)           C(5B)-C(1B)-Fe(1)-C(9)                              -30(5)           C(2B)-C(1B)-Fe(1)-C(9)                             -149(4)           C(5B)-C(1B)-Fe(1)-C(1)                              -13(11)           C(2B)-C(1B)-Fe(1)-C(1)                             -132(13)           C(5B)-C(1B)-Fe(1)-C(2B)                             119(2)           C(5B)-C(1B)-Fe(1)-C(6)                             -111.3(14)           C(2B)-C(1B)-Fe(1)-C(6)                              129.7(12)           C(2B)-C(1B)-Fe(1)-C(5B)                            -119(2)           C(5B)-C(1B)-Fe(1)-C(8)                              168.5(13)           C(2B)-C(1B)-Fe(1)-C(8)                               50(2)           C(5B)-C(1B)-Fe(1)-C(4)                               44.5(15)           C(2B)-C(1B)-Fe(1)-C(4)                              -74.4(15)           C(4B)-C(5B)-Fe(1)-C(3)                               46.1(12)           C(1B)-C(5B)-Fe(1)-C(3)                              -74.0(15)           C(4B)-C(5B)-Fe(1)-C(10)                            -108.9(10)           C(1B)-C(5B)-Fe(1)-C(10)                             131.1(14)           C(1B)-C(5B)-Fe(1)-C(4B)                            -120.1(19)           C(4B)-C(5B)-Fe(1)-C(5)                              -26(8)           C(1B)-C(5B)-Fe(1)-C(5)                             -146(9)           C(4B)-C(5B)-Fe(1)-C(9)                              -67.1(13)           C(1B)-C(5B)-Fe(1)-C(9)                              172.8(13)           C(4B)-C(5B)-Fe(1)-C(1)                              124(3)           C(1B)-C(5B)-Fe(1)-C(1)                                4(3)           C(4B)-C(5B)-Fe(1)-C(2B)                              81.9(12)           C(1B)-C(5B)-Fe(1)-C(2B)                             -38.2(15)           C(4B)-C(5B)-Fe(1)-C(6)                             -153.1(9)           C(1B)-C(5B)-Fe(1)-C(6)                               86.8(15)           C(4B)-C(5B)-Fe(1)-C(1B)                             120.1(19)           C(4B)-C(5B)-Fe(1)-C(8)                              -31(4)           C(1B)-C(5B)-Fe(1)-C(8)                             -151(3)           C(4B)-C(5B)-Fe(1)-C(4)                                5.4(16)           C(1B)-C(5B)-Fe(1)-C(4)                             -114.7(19)           C(7)-C(8)-Fe(1)-C(3)                                123.2(8)           C(9)-C(8)-Fe(1)-C(3)                               -117.0(8)           C(7)-C(8)-Fe(1)-C(10)                               -81.38(11)           C(9)-C(8)-Fe(1)-C(10)                                38.45(11)           C(7)-C(8)-Fe(1)-C(4B)                               171.0(7) 189            C(9)-C(8)-Fe(1)-C(4B)                               -69.2(7)           C(7)-C(8)-Fe(1)-C(5)                               -166(2)           C(9)-C(8)-Fe(1)-C(5)                                -46(2)           C(7)-C(8)-Fe(1)-C(9)                               -119.83(16)           C(7)-C(8)-Fe(1)-C(1)                                 54(3)           C(9)-C(8)-Fe(1)-C(1)                                174(3)           C(7)-C(8)-Fe(1)-C(2B)                                88.5(6)           C(9)-C(8)-Fe(1)-C(2B)                              -151.7(6)           C(7)-C(8)-Fe(1)-C(6)                                -36.85(11)           C(9)-C(8)-Fe(1)-C(6)                                 82.98(12)           C(7)-C(8)-Fe(1)-C(1B)                                54.8(17)           C(9)-C(8)-Fe(1)-C(1B)                               174.6(17)           C(7)-C(8)-Fe(1)-C(5B)                              -163(3)           C(9)-C(8)-Fe(1)-C(5B)                               -44(3)           C(7)-C(8)-Fe(1)-C(4)                                165.3(9)           C(9)-C(8)-Fe(1)-C(4)                                -74.9(9)           C(5)-C(4)-Fe(1)-C(3)                               -119.2(19)           C(5)-C(4)-Fe(1)-C(10)                                80.5(14)           C(3)-C(4)-Fe(1)-C(10)                              -160.4(12)           C(5)-C(4)-Fe(1)-C(4B)                                21(8)           C(3)-C(4)-Fe(1)-C(4B)                               140(9)           C(3)-C(4)-Fe(1)-C(5)                                119.2(19)           C(5)-C(4)-Fe(1)-C(9)                                122.9(13)           C(3)-C(4)-Fe(1)-C(9)                               -117.9(13)           C(5)-C(4)-Fe(1)-C(1)                                -37.8(14)           C(3)-C(4)-Fe(1)-C(1)                                 81.4(16)           C(5)-C(4)-Fe(1)-C(2B)                               -90.0(14)           C(3)-C(4)-Fe(1)-C(2B)                                29.2(14)           C(5)-C(4)-Fe(1)-C(6)                                 49(2)           C(3)-C(4)-Fe(1)-C(6)                                167.7(14)           C(5)-C(4)-Fe(1)-C(1B)                               -46.1(14)           C(3)-C(4)-Fe(1)-C(1B)                                73.1(14)           C(5)-C(4)-Fe(1)-C(5B)                                -7.7(17)           C(3)-C(4)-Fe(1)-C(5B)                               111.5(17)           C(5)-C(4)-Fe(1)-C(8)                                163.8(11)           C(3)-C(4)-Fe(1)-C(8)                                -77.0(14)          ________________________________________________________________   Table 7.  Hydrogen Bonds  Donor --- H....Acceptor [    ARU  ]      D - H      H...A      D...A  D - H...A     -------------------------------------------------------------------------------- O3    --H3O    ..O1     [  1655.01]    0.91(6)    1.87(6)   2.778(3)   177(5)    Translation of ARU-code to Equivalent Position Code ===================================================    [  1655. ]  = 1+x,y,z       190  8.2 X-ray structure report for complex 3.3 Data Collection  A red prism crystal of C25H18O10FeCo2 having approximate dimensions of 0.22 x 0.25 x 0.40 mm was mounted on a glass fiber. All measurements were made on a Bruker X8 APEX II diffractometer with graphite monochromated Mo-Kα radiation.  The data were collected at a temperature of -100.0 + 0.1oC to a maximum 2θ value of 56.0o. Data were collected in a series of φ and ω scans in 0.50o oscillations with 5.0-second exposures. The crystal-to-detector distance was 36.00 mm.  Data Reduction  Of the 27275 reflections that were collected, 6187 were unique (Rint = 0.026); equivalent reflections were merged.  Data were collected and integrated using the Bruker SAINT1 software package. The linear absorption coefficient, µ, for Mo-Kα radiation is 18.85 cm-1. Data were corrected for absorption effects using the multi-scan technique (SADABS2), with minimum and maximum transmission coefficients of 0.560 and 0.661, respectively.  The data were corrected for Lorentz and polarization effects.  Structure Solution and Refinement  The structure was solved by direct methods3.   The material crystallizes with disorder about the C16 – C17 bond, with the acetylenic and methyl carbons exchanging positions.  All non-hydrogen atoms were refined anisotropically.  All C-H hydrogen atoms were placed in calculated positions but were not refined.  The final cycle of full-matrix least-squares refinement4 on F2 was based on 6187 reflections and 364 variable parameters and converged (largest parameter shift was 0.00 times its esd) with unweighted and weighted agreement factors of:  191  R1 = Σ ||Fo| - |Fc|| / Σ |Fo| = 0.033 wR2 = [ Σ ( w (Fo2 - Fc2)2 )/ Σ w(Fo2)2]1/2 = 0.059  The standard deviation of an observation of unit weight5 was 1.02. The weighting scheme was based on counting statistics.  The maximum and minimum peaks on the final difference Fourier map corresponded to 0.32 and –0.32 e-/Å3, respectively.  Neutral atom scattering factors were taken from Cromer and Waber6. Anomalous dispersion effects were included in Fcalc7; the values for ∆f' and ∆f" were those of Creagh and McAuley8. The values for the mass attenuation coefficients are those of Creagh and Hubbell9. All refinements were performed using the SHELXTL10 crystallographic software package of Bruker-AXS. References  (1) SAINT. Version 7.60A. Bruker AXS Inc., Madison, Wisconsin, USA. (1997-2009).   (2) SADABS. Bruker Nonius area detector scaling and absorption correction - V2008/1, Bruker AXS Inc., Madison, Wisconsin, USA (2008).  (3) SIR97 - Altomare A., Burla M.C., Camalli M., Cascarano G.L., Giacovazzo C. , Guagliardi A., Moliterni A.G.G., Polidori G.,Spagna R. (1999) J. Appl. Cryst. 32, 115-119.   (4) Least Squares function minimized:   Σw(Fo2-Fc2)2 (5) Standard deviation of an observation of unit weight:       [Σw(Fo2-Fc2)2/(No-Nv)]1/2 192      where: No  = number of observations         Nv  = number of variables   (6) Cromer, D. T. & Waber, J. T.; "International Tables for X-ray Crystallography", Vol. IV, The Kynoch Press, Birmingham, England, Table 2.2 A (1974).   (7) Ibers, J. A. & Hamilton, W. C.; Acta Crystallogr., 17, 781 (1964).   (8) Creagh, D. C. & McAuley, W.J .; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.6.8, pages 219-222 (1992).   (9) Creagh, D. C. & Hubbell, J.H..; "International Tables for Crystallography", Vol C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.4.3, pages 200-206 (1992).   (10) SHELXTL Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA. (1997).    EXPERIMENTAL DETAILS  A. Crystal Data  Empirical Formula C25H18O10FeCo2 Formula Weight 652.10 Crystal Color, Habit red, prism Crystal Dimensions 0.22 X 0.25 X 0.40 mm Crystal System monoclinic 193  Lattice Type primitive Lattice Parameters a = 13.7682(4) Å  b = 12.9640(4) Å  c = 15.5095(5) Å  α = 90 o  β = 111.513(1) o  γ = 90o  V = 2575.45(4) Å3 Space Group P 21/n (#14) Z value 4 Dcalc 1.682 g/cm3 F000 1312.00 µ(MoKα) 18.85 cm-1 B. Intensity Measurements  Diffractometer Bruker X8 APEX II Radiation MoKα (λ = 0.71073 Å)  graphite monochromated Data Images 1233 exposures @ 5.0 seconds Detector Position 36.00 mm 2θmax 56.1o  No. of Reflections Measured Total: 27275   Unique: 6187 (Rint = 0.026) 194  Corrections Absorption (Tmin = 0.560, Tmax= 0.661)  Lorentz-polarization C. Structure Solution and Refinement  Structure Solution Direct Methods (SIR97) Refinement Full-matrix least-squares on F2 Function Minimized Σ w (Fo2 - Fc2)2  Least Squares Weights w=1/(σ2(Fo2)+(0.0270P) 2+ 0.8904P) Anomalous Dispersion All non-hydrogen atoms No. Observations (I>0.00σ(I)) 6187 No. Variables 364 Reflection/Parameter Ratio 17.00 Residuals (refined on F2, all data): R1; wR2 0.033; 0.059 Goodness of Fit Indicator 1.02 No. Observations (I>2.00σ(I)) 5213 Residuals (refined on F): R1; wR2 0.023; 0.056 Max Shift/Error in Final Cycle 0.00 Maximum peak in Final Diff. Map 0.32 e-/Å3 Minimum peak in Final Diff. Map -0.32 e-/Å3 195           Table 2.  Atomic coordinates ( x 10^4) and equivalent isotropic          displacement parameters (A^2 x 10^3) for aa001_0m.          U(eq) is defined as one third of the trace of the orthogonalized          Uij tensor.            ________________________________________________________________                            x             y             z           U(eq) occ          ________________________________________________________________        C(1)         5465(2)       2939(2)      -3651(2)       61(1)      C(2)         6178(2)       2842(2)      -2727(2)       48(1)      C(3)         7170(2)       2770(2)      -2753(2)       55(1)      C(4)         7088(3)       2820(2)      -3668(2)       73(1)      C(5)         6044(3)       2924(2)      -4228(2)       75(1)      C(6)         6258(1)       5344(1)      -2600(1)       28(1)      C(7)         5674(1)       5487(1)      -3557(1)       34(1)      C(8)         6374(1)       5494(1)      -4035(1)       34(1)      C(9)         7401(1)       5359(1)      -3383(1)       28(1)      C(10)        7333(1)       5262(1)      -2489(1)       23(1)      C(11)        8211(1)       5011(1)      -1637(1)       23(1)      C(12)        8690(1)       4537(2)        -62(1)       28(1)      C(13)        8217(1)       4542(1)        653(1)       23(1)      C(14)        8419(1)       4366(1)       1552(1)       24(1)      C(15)        9247(1)       4001(2)       2414(1)       30(1)      C(16)        9517(1)       3744(1)       3986(1)       30(1)      C(17)        9097(2)       3893(1)       4738(1)       31(1) 0.59(2)      C(18)        9848(14)      3687(15)      5671(6)       41(3) 0.59(2)      C(19)        8096(10)      4186(12)      4548(11)      52(3) 0.59(2)      C(17B)       9097(2)       3893(1)       4738(1)       31(1) 0.41(2)      C(18B)       7996(10)      4177(17)      4465(13)      40(4) 0.41(2)      C(19B)       9760(20)      3760(20)      5622(10)      45(5) 0.41(2)      C(20)        5926(1)       4072(1)       -276(1)       29(1)      C(21)        7348(1)       2585(1)        561(1)       32(1)      C(22)        6464(1)       3686(2)       1685(1)       35(1)      C(23)        6743(1)       6228(1)        108(1)       32(1)      C(24)        8757(2)       6526(2)       1432(1)       39(1)      C(25)        7175(2)       5987(2)       2074(1)       38(1)      O(1)         9116(1)       4950(1)      -1561(1)       35(1)      O(2)         7887(1)       4839(1)       -928(1)       26(1)      O(3)         8859(1)       4088(1)       3159(1)       29(1)      O(4)        10351(1)       3372(1)       4096(1)       55(1)      O(5)         5251(1)       4210(1)       -957(1)       45(1)      O(6)         7612(1)       1808(1)        394(1)       49(1)      O(7)         6140(1)       3604(1)       2254(1)       58(1)      O(8)         6163(1)       6518(1)       -574(1)       45(1)      O(9)         9468(1)       7037(1)       1585(1)       62(1)      O(10)        6868(1)       6184(1)       2634(1)       63(1)      Fe(1)        6497(1)       4127(1)      -3327(1)       24(1)      Co(1)        7027(1)       3868(1)        802(1)       22(1)      Co(2)        7661(1)       5663(1)       1165(1)       25(1)          196     ________________________________________________________________             Table 3.  Bond lengths [A] and angles [deg] for aa001_0m.            _____________________________________________________________               C(1)-C(5)                     1.402(4)             C(1)-C(2)                     1.415(3)             C(1)-Fe(1)                    2.030(2)             C(1)-H(1)                     0.9500             C(2)-C(3)                     1.384(3)             C(2)-Fe(1)                    2.0331(19)             C(2)-H(2)                     0.9500             C(3)-C(4)                     1.383(4)             C(3)-Fe(1)                    2.034(2)             C(3)-H(3)                     0.9500             C(4)-C(5)                     1.386(4)             C(4)-Fe(1)                    2.032(2)             C(4)-H(4)                     0.9500             C(5)-Fe(1)                    2.034(2)             C(5)-H(5)                     0.9500             C(6)-C(7)                     1.416(2)             C(6)-C(10)                    1.429(2)             C(6)-Fe(1)                    2.0342(16)             C(6)-H(6)                     0.9500             C(7)-C(8)                     1.415(3)             C(7)-Fe(1)                    2.0548(18)             C(7)-H(7)                     0.9500             C(8)-C(9)                     1.416(2)             C(8)-Fe(1)                    2.0596(17)             C(8)-H(8)                     0.9500             C(9)-C(10)                    1.429(2)             C(9)-Fe(1)                    2.0465(16)             C(9)-H(9)                     0.9500             C(10)-C(11)                   1.465(2)             C(10)-Fe(1)                   2.0194(15)             C(11)-O(1)                    1.2099(18)             C(11)-O(2)                    1.3480(17)             C(12)-O(2)                    1.4456(18)             C(12)-C(13)                   1.477(2)             C(12)-H(12A)                  0.9900             C(12)-H(12B)                  0.9900             C(13)-C(14)                   1.338(2)             C(13)-Co(2)                   1.9436(15)             C(13)-Co(1)                   1.9444(15)             C(14)-C(15)                   1.481(2)             C(14)-Co(1)                   1.9518(15)             C(14)-Co(2)                   1.9550(16)             C(15)-O(3)                    1.4438(18)             C(15)-H(15A)                  0.9900             C(15)-H(15B)                  0.9900             C(16)-O(4)                    1.199(2)             C(16)-O(3)                    1.3459(19)             C(16)-C(17)                   1.491(2)             C(17)-C(19)                   1.354(12)             C(17)-C(18)                   1.462(11)             C(18)-H(18A)                  0.9800             C(18)-H(18B)                  0.9800             C(18)-H(18C)                  0.9800 197              C(19)-H(19A)                  0.9500             C(19)-H(19B)                  0.9500             C(18B)-H(18D)                 0.9800             C(18B)-H(18E)                 0.9800             C(18B)-H(18F)                 0.9800             C(19B)-H(19C)                 0.9500             C(19B)-H(19D)                 0.9500             C(20)-O(5)                    1.135(2)             C(20)-Co(1)                   1.8174(17)             C(21)-O(6)                    1.132(2)             C(21)-Co(1)                   1.7962(19)             C(22)-O(7)                    1.131(2)             C(22)-Co(1)                   1.8196(17)             C(23)-O(8)                    1.131(2)             C(23)-Co(2)                   1.8163(18)             C(24)-O(9)                    1.133(2)             C(24)-Co(2)                   1.800(2)             C(25)-O(10)                   1.126(2)             C(25)-Co(2)                   1.8182(18)             Co(1)-Co(2)                   2.4767(3)               C(5)-C(1)-C(2)              107.4(2)             C(5)-C(1)-Fe(1)              69.98(13)             C(2)-C(1)-Fe(1)              69.75(11)             C(5)-C(1)-H(1)              126.3             C(2)-C(1)-H(1)              126.3             Fe(1)-C(1)-H(1)             125.6             C(3)-C(2)-C(1)              107.6(2)             C(3)-C(2)-Fe(1)              70.16(12)             C(1)-C(2)-Fe(1)              69.48(12)             C(3)-C(2)-H(2)              126.2             C(1)-C(2)-H(2)              126.2             Fe(1)-C(2)-H(2)             125.7             C(4)-C(3)-C(2)              108.5(2)             C(4)-C(3)-Fe(1)              70.03(14)             C(2)-C(3)-Fe(1)              70.07(12)             C(4)-C(3)-H(3)              125.7             C(2)-C(3)-H(3)              125.7             Fe(1)-C(3)-H(3)             125.8             C(3)-C(4)-C(5)              108.8(2)             C(3)-C(4)-Fe(1)              70.20(13)             C(5)-C(4)-Fe(1)              70.13(14)             C(3)-C(4)-H(4)              125.6             C(5)-C(4)-H(4)              125.6             Fe(1)-C(4)-H(4)             125.7             C(4)-C(5)-C(1)              107.6(2)             C(4)-C(5)-Fe(1)              70.00(14)             C(1)-C(5)-Fe(1)              69.66(13)             C(4)-C(5)-H(5)              126.2             C(1)-C(5)-H(5)              126.2             Fe(1)-C(5)-H(5)             125.8             C(7)-C(6)-C(10)             107.50(14)             C(7)-C(6)-Fe(1)              70.51(10)             C(10)-C(6)-Fe(1)             68.80(9)             C(7)-C(6)-H(6)              126.3             C(10)-C(6)-H(6)             126.3             Fe(1)-C(6)-H(6)             126.0 198              C(8)-C(7)-C(6)              108.44(15)             C(8)-C(7)-Fe(1)              70.07(10)             C(6)-C(7)-Fe(1)              68.96(10)             C(8)-C(7)-H(7)              125.8             C(6)-C(7)-H(7)              125.8             Fe(1)-C(7)-H(7)             126.8             C(7)-C(8)-C(9)              108.52(14)             C(7)-C(8)-Fe(1)              69.70(10)             C(9)-C(8)-Fe(1)              69.33(9)             C(7)-C(8)-H(8)              125.7             C(9)-C(8)-H(8)              125.7             Fe(1)-C(8)-H(8)             126.8             C(8)-C(9)-C(10)             107.49(14)             C(8)-C(9)-Fe(1)              70.33(9)             C(10)-C(9)-Fe(1)             68.42(9)             C(8)-C(9)-H(9)              126.3             C(10)-C(9)-H(9)             126.3             Fe(1)-C(9)-H(9)             126.6             C(9)-C(10)-C(6)             108.05(13)             C(9)-C(10)-C(11)            124.69(14)             C(6)-C(10)-C(11)            126.96(13)             C(9)-C(10)-Fe(1)             70.45(9)             C(6)-C(10)-Fe(1)             69.91(9)             C(11)-C(10)-Fe(1)           120.41(11)             O(1)-C(11)-O(2)             123.16(14)             O(1)-C(11)-C(10)            125.63(14)             O(2)-C(11)-C(10)            111.20(12)             O(2)-C(12)-C(13)            107.39(12)             O(2)-C(12)-H(12A)           110.2             C(13)-C(12)-H(12A)          110.2             O(2)-C(12)-H(12B)           110.2             C(13)-C(12)-H(12B)          110.2             H(12A)-C(12)-H(12B)         108.5             C(14)-C(13)-C(12)           143.25(14)             C(14)-C(13)-Co(2)            70.39(9)             C(12)-C(13)-Co(2)           131.18(12)             C(14)-C(13)-Co(1)            70.22(9)             C(12)-C(13)-Co(1)           135.20(12)             Co(2)-C(13)-Co(1)            79.14(5)             C(13)-C(14)-C(15)           142.47(14)             C(13)-C(14)-Co(1)            69.62(9)             C(15)-C(14)-Co(1)           134.03(13)             C(13)-C(14)-Co(2)            69.48(10)             C(15)-C(14)-Co(2)           134.41(12)             Co(1)-C(14)-Co(2)            78.68(6)             O(3)-C(15)-C(14)            108.06(12)             O(3)-C(15)-H(15A)           110.1             C(14)-C(15)-H(15A)          110.1             O(3)-C(15)-H(15B)           110.1             C(14)-C(15)-H(15B)          110.1             H(15A)-C(15)-H(15B)         108.4             O(4)-C(16)-O(3)             122.92(15)             O(4)-C(16)-C(17)            124.51(16)             O(3)-C(16)-C(17)            112.56(14)             C(19)-C(17)-C(18)           124.1(9)             C(19)-C(17)-C(16)           121.4(6)             C(18)-C(17)-C(16)           114.5(7) 199              C(17)-C(19)-H(19A)          120.0             C(17)-C(19)-H(19B)          120.0             H(19A)-C(19)-H(19B)         120.0             H(18D)-C(18B)-H(18E)        109.5             H(18D)-C(18B)-H(18F)        109.5             H(18E)-C(18B)-H(18F)        109.5             H(19C)-C(19B)-H(19D)        120.0             O(5)-C(20)-Co(1)            178.62(16)             O(6)-C(21)-Co(1)            174.69(16)             O(7)-C(22)-Co(1)            177.24(18)             O(8)-C(23)-Co(2)            175.56(16)             O(9)-C(24)-Co(2)            176.99(18)             O(10)-C(25)-Co(2)           179.5(2)             C(11)-O(2)-C(12)            115.66(11)             C(16)-O(3)-C(15)            114.81(12)             C(10)-Fe(1)-C(1)            153.37(9)             C(10)-Fe(1)-C(4)            125.90(11)             C(1)-Fe(1)-C(4)              67.31(12)             C(10)-Fe(1)-C(2)            118.05(7)             C(1)-Fe(1)-C(2)              40.77(9)             C(4)-Fe(1)-C(2)              67.08(10)             C(10)-Fe(1)-C(5)            163.58(11)             C(1)-Fe(1)-C(5)              40.37(11)             C(4)-Fe(1)-C(5)              39.88(12)             C(2)-Fe(1)-C(5)              67.88(9)             C(10)-Fe(1)-C(6)             41.29(6)             C(1)-Fe(1)-C(6)             119.00(10)             C(4)-Fe(1)-C(6)             162.26(11)             C(2)-Fe(1)-C(6)             106.04(8)             C(5)-Fe(1)-C(6)             154.77(12)             C(10)-Fe(1)-C(3)            106.74(8)             C(1)-Fe(1)-C(3)              67.51(10)             C(4)-Fe(1)-C(3)              39.77(11)             C(2)-Fe(1)-C(3)              39.77(9)             C(5)-Fe(1)-C(3)              67.24(11)             C(6)-Fe(1)-C(3)             124.66(9)             C(10)-Fe(1)-C(9)             41.13(6)             C(1)-Fe(1)-C(9)             164.41(9)             C(4)-Fe(1)-C(9)             109.36(10)             C(2)-Fe(1)-C(9)             153.61(8)             C(5)-Fe(1)-C(9)             127.36(9)             C(6)-Fe(1)-C(9)              69.05(7)             C(3)-Fe(1)-C(9)             120.47(8)             C(10)-Fe(1)-C(7)             68.56(7)             C(1)-Fe(1)-C(7)             108.47(9)             C(4)-Fe(1)-C(7)             156.64(11)             C(2)-Fe(1)-C(7)             125.81(9)             C(5)-Fe(1)-C(7)             121.89(11)             C(6)-Fe(1)-C(7)              40.53(7)             C(3)-Fe(1)-C(7)             162.07(9)             C(9)-Fe(1)-C(7)              68.15(7)             C(10)-Fe(1)-C(8)             68.43(6)             C(1)-Fe(1)-C(8)             127.42(9)             C(4)-Fe(1)-C(8)             122.73(10)             C(2)-Fe(1)-C(8)             163.78(9)             C(5)-Fe(1)-C(8)             110.39(9)             C(6)-Fe(1)-C(8)              68.26(7) 200              C(3)-Fe(1)-C(8)             155.86(9)             C(9)-Fe(1)-C(8)              40.34(7)             C(7)-Fe(1)-C(8)              40.23(7)             C(21)-Co(1)-C(20)            97.46(8)             C(21)-Co(1)-C(22)           103.97(8)             C(20)-Co(1)-C(22)           105.67(7)             C(21)-Co(1)-C(13)            96.25(7)             C(20)-Co(1)-C(13)           106.29(7)             C(22)-Co(1)-C(13)           139.26(7)             C(21)-Co(1)-C(14)            99.60(7)             C(20)-Co(1)-C(14)           143.69(7)             C(22)-Co(1)-C(14)           100.95(7)             C(13)-Co(1)-C(14)            40.16(6)             C(21)-Co(1)-Co(2)           145.56(6)             C(20)-Co(1)-Co(2)           100.24(6)             C(22)-Co(1)-Co(2)            99.34(6)             C(13)-Co(1)-Co(2)            50.42(5)             C(14)-Co(1)-Co(2)            50.72(5)             C(24)-Co(2)-C(23)           101.80(9)             C(24)-Co(2)-C(25)           101.16(9)             C(23)-Co(2)-C(25)           105.98(8)             C(24)-Co(2)-C(13)            97.80(7)             C(23)-Co(2)-C(13)           100.42(7)             C(25)-Co(2)-C(13)           143.32(8)             C(24)-Co(2)-C(14)            98.92(8)             C(23)-Co(2)-C(14)           137.77(7)             C(25)-Co(2)-C(14)           105.51(8)             C(13)-Co(2)-C(14)            40.13(6)             C(24)-Co(2)-Co(1)           146.26(6)             C(23)-Co(2)-Co(1)            95.93(6)             C(25)-Co(2)-Co(1)           101.20(6)             C(13)-Co(2)-Co(1)            50.45(4)             C(14)-Co(2)-Co(1)            50.60(5)            _____________________________________________________________              Symmetry transformations used to generate equivalent atoms:      201      Table 4.  Anisotropic displacement parameters (A^2 x 10^3) for aa001_0m.     The anisotropic displacement factor exponent takes the form:     -2 pi^2 [ h^2 a*^2 U11 + ... + 2 h k a* b* U12 ]       _______________________________________________________________________                 U11        U22        U33        U23        U13        U12     _______________________________________________________________________       C(1)     51(1)      38(1)      74(2)       1(1)       1(1)     -22(1)     C(2)     74(2)      31(1)      43(1)       4(1)      26(1)     -18(1)     C(3)     58(1)      22(1)      71(2)      10(1)       6(1)       1(1)     C(4)    115(2)      28(1)     106(2)      -7(1)      76(2)       6(1)     C(5)    153(3)      30(1)      32(1)     -12(1)      22(2)     -24(2)     C(6)     28(1)      30(1)      24(1)      -2(1)       8(1)       4(1)     C(7)     32(1)      32(1)      30(1)       2(1)       1(1)       7(1)     C(8)     47(1)      27(1)      21(1)       5(1)       5(1)      -5(1)     C(9)     36(1)      26(1)      22(1)       0(1)      11(1)      -8(1)     C(10)    27(1)      20(1)      20(1)      -1(1)       8(1)      -3(1)     C(11)    26(1)      26(1)      20(1)      -2(1)      10(1)      -4(1)     C(12)    19(1)      48(1)      16(1)       3(1)       7(1)       4(1)     C(13)    18(1)      30(1)      21(1)      -1(1)       8(1)       1(1)     C(14)    20(1)      31(1)      21(1)      -1(1)       7(1)       2(1)     C(15)    24(1)      49(1)      19(1)       3(1)       9(1)      10(1)     C(16)    37(1)      30(1)      21(1)       2(1)       6(1)       3(1)     C(17)    46(1)      26(1)      21(1)       1(1)      12(1)      -5(1)     C(18)    58(5)      43(6)      14(3)       1(3)       2(3)      -8(4)     C(19)    71(6)      66(7)      19(3)      10(3)      18(3)      12(5)     C(17B)   46(1)      26(1)      21(1)       1(1)      12(1)      -5(1)     C(18B)   37(5)      60(9)      39(9)      -3(5)      31(5)       1(4)     C(19B)   58(7)      32(7)      50(10)      5(6)      28(7)      -8(6)     C(20)    23(1)      33(1)      31(1)       1(1)      12(1)      -2(1)     C(21)    29(1)      35(1)      28(1)       1(1)       6(1)       0(1)     C(22)    29(1)      44(1)      31(1)       3(1)      11(1)      -6(1)     C(23)    35(1)      25(1)      35(1)       0(1)      14(1)       4(1)     C(24)    42(1)      36(1)      41(1)      -6(1)      17(1)      -3(1)     C(25)    37(1)      43(1)      32(1)      -7(1)      12(1)       2(1)     O(1)     23(1)      61(1)      24(1)       2(1)      11(1)      -2(1)     O(2)     19(1)      44(1)      16(1)       2(1)       6(1)       2(1)     O(3)     28(1)      41(1)      17(1)       4(1)      10(1)       7(1)     O(4)     49(1)      81(1)      28(1)      10(1)       7(1)      33(1)     O(5)     29(1)      62(1)      35(1)       8(1)       1(1)       1(1)     O(6)     53(1)      37(1)      52(1)      -8(1)      13(1)       9(1)     O(7)     51(1)      92(1)      41(1)       5(1)      29(1)     -15(1)     O(8)     49(1)      38(1)      40(1)       7(1)       8(1)      14(1)     O(9)     55(1)      50(1)      86(1)     -21(1)      32(1)     -23(1)     O(10)    65(1)      91(1)      43(1)     -21(1)      31(1)       7(1)     Fe(1)    29(1)      21(1)      20(1)       0(1)       8(1)      -3(1)     Co(1)    20(1)      27(1)      20(1)       1(1)       8(1)       1(1)     Co(2)    25(1)      28(1)      22(1)      -2(1)      10(1)       0(1)     _______________________________________________________________________    202           Table 5.  Hydrogen coordinates ( x 10^4) and isotropic          displacement parameters (A^2 x 10^3) for aa001_0m.            ________________________________________________________________                            x             y             z           U(eq)          ________________________________________________________________             H(1)         4728          3003         -3844          73           H(2)         6008          2828         -2186          58           H(3)         7800          2699         -2231          66           H(4)         7655          2789         -3878          87           H(5)         5772          2976         -4885          90           H(6)         5985          5309         -2120          34           H(7)         4938          5565         -3830          41           H(8)         6186          5576         -4685          40           H(9)         8022          5338         -3515          33           H(12A)       9282          5027           106          34           H(12B)       8952          3839          -118          34           H(15A)       9425          3274          2343          36           H(15B)       9884          4425          2551          36           H(18A)       9525          3837          6125          61           H(18B)      10463          4127          5794          61           H(18C)      10058          2961          5720          61           H(19A)       7843          4269          5037          62           H(19B)       7646          4308          3925          62           H(18D)       7820          4249          5020          60           H(18E)       7559          3638          4064          60           H(18F)       7870          4833          4128          60           H(19C)       9523          3860          6119          53           H(19D)      10468          3580          5747          53          ________________________________________________________________    203           Table 6.  Torsion angles [deg] for aa001_0m.          ________________________________________________________________             C(5)-C(1)-C(2)-C(3)                                   0.0(2)           Fe(1)-C(1)-C(2)-C(3)                                -60.09(15)           C(5)-C(1)-C(2)-Fe(1)                                 60.12(15)           C(1)-C(2)-C(3)-C(4)                                   0.0(2)           Fe(1)-C(2)-C(3)-C(4)                                -59.67(16)           C(1)-C(2)-C(3)-Fe(1)                                 59.66(15)           C(2)-C(3)-C(4)-C(5)                                   0.0(3)           Fe(1)-C(3)-C(4)-C(5)                                -59.71(17)           C(2)-C(3)-C(4)-Fe(1)                                 59.70(15)           C(3)-C(4)-C(5)-C(1)                                   0.0(3)           Fe(1)-C(4)-C(5)-C(1)                                -59.73(16)           C(3)-C(4)-C(5)-Fe(1)                                 59.75(16)           C(2)-C(1)-C(5)-C(4)                                   0.0(3)           Fe(1)-C(1)-C(5)-C(4)                                 59.94(17)           C(2)-C(1)-C(5)-Fe(1)                                -59.98(15)           C(10)-C(6)-C(7)-C(8)                                  0.0(2)           Fe(1)-C(6)-C(7)-C(8)                                -59.11(13)           C(10)-C(6)-C(7)-Fe(1)                                59.08(11)           C(6)-C(7)-C(8)-C(9)                                  -0.2(2)           Fe(1)-C(7)-C(8)-C(9)                                -58.61(12)           C(6)-C(7)-C(8)-Fe(1)                                 58.43(13)           C(7)-C(8)-C(9)-C(10)                                  0.3(2)           Fe(1)-C(8)-C(9)-C(10)                               -58.52(11)           C(7)-C(8)-C(9)-Fe(1)                                 58.84(13)           C(8)-C(9)-C(10)-C(6)                                 -0.34(19)           Fe(1)-C(9)-C(10)-C(6)                               -60.06(11)           C(8)-C(9)-C(10)-C(11)                               173.77(15)           Fe(1)-C(9)-C(10)-C(11)                              114.05(16)           C(8)-C(9)-C(10)-Fe(1)                                59.72(12)           C(7)-C(6)-C(10)-C(9)                                  0.23(19)           Fe(1)-C(6)-C(10)-C(9)                                60.40(11)           C(7)-C(6)-C(10)-C(11)                              -173.71(16)           Fe(1)-C(6)-C(10)-C(11)                             -113.54(16)           C(7)-C(6)-C(10)-Fe(1)                               -60.17(12)           C(9)-C(10)-C(11)-O(1)                                 7.3(3)           C(6)-C(10)-C(11)-O(1)                              -179.71(17)           Fe(1)-C(10)-C(11)-O(1)                               93.54(19)           C(9)-C(10)-C(11)-O(2)                              -171.95(15)           C(6)-C(10)-C(11)-O(2)                                 1.0(2)           Fe(1)-C(10)-C(11)-O(2)                              -85.72(15)           O(2)-C(12)-C(13)-C(14)                              179.6(2)           O(2)-C(12)-C(13)-Co(2)                              -65.14(18)           O(2)-C(12)-C(13)-Co(1)                               56.6(2)           C(12)-C(13)-C(14)-C(15)                              -3.9(4)           Co(2)-C(13)-C(14)-C(15)                            -137.7(3)           Co(1)-C(13)-C(14)-C(15)                             137.2(3)           C(12)-C(13)-C(14)-Co(1)                            -141.1(3)           Co(2)-C(13)-C(14)-Co(1)                              85.16(4)           C(12)-C(13)-C(14)-Co(2)                             133.7(3)           Co(1)-C(13)-C(14)-Co(2)                             -85.16(4)           C(13)-C(14)-C(15)-O(3)                              176.9(2)           Co(1)-C(14)-C(15)-O(3)                              -65.5(2)           Co(2)-C(14)-C(15)-O(3)                               58.9(2)           O(4)-C(16)-C(17)-C(19)                             -170.8(8) 204            O(3)-C(16)-C(17)-C(19)                               10.1(8)           O(4)-C(16)-C(17)-C(18)                                8.6(8)           O(3)-C(16)-C(17)-C(18)                             -170.5(8)           O(1)-C(11)-O(2)-C(12)                                -2.1(2)           C(10)-C(11)-O(2)-C(12)                              177.18(14)           C(13)-C(12)-O(2)-C(11)                              171.49(14)           O(4)-C(16)-O(3)-C(15)                                -1.6(3)           C(17)-C(16)-O(3)-C(15)                              177.55(14)           C(14)-C(15)-O(3)-C(16)                              177.50(14)           C(9)-C(10)-Fe(1)-C(1)                              -169.52(18)           C(6)-C(10)-Fe(1)-C(1)                               -50.8(2)           C(11)-C(10)-Fe(1)-C(1)                               71.0(2)           C(9)-C(10)-Fe(1)-C(4)                                78.06(14)           C(6)-C(10)-Fe(1)-C(4)                              -163.25(13)           C(11)-C(10)-Fe(1)-C(4)                              -41.40(16)           C(9)-C(10)-Fe(1)-C(2)                               158.90(11)           C(6)-C(10)-Fe(1)-C(2)                               -82.41(12)           C(11)-C(10)-Fe(1)-C(2)                               39.44(15)           C(9)-C(10)-Fe(1)-C(5)                                51.6(3)           C(6)-C(10)-Fe(1)-C(5)                               170.2(3)           C(11)-C(10)-Fe(1)-C(5)                              -67.9(3)           C(9)-C(10)-Fe(1)-C(6)                              -118.68(14)           C(11)-C(10)-Fe(1)-C(6)                              121.85(16)           C(9)-C(10)-Fe(1)-C(3)                               117.42(12)           C(6)-C(10)-Fe(1)-C(3)                              -123.89(11)           C(11)-C(10)-Fe(1)-C(3)                               -2.04(15)           C(6)-C(10)-Fe(1)-C(9)                               118.68(14)           C(11)-C(10)-Fe(1)-C(9)                             -119.46(16)           C(9)-C(10)-Fe(1)-C(7)                               -80.90(11)           C(6)-C(10)-Fe(1)-C(7)                                37.79(10)           C(11)-C(10)-Fe(1)-C(7)                              159.64(14)           C(9)-C(10)-Fe(1)-C(8)                               -37.51(10)           C(6)-C(10)-Fe(1)-C(8)                                81.18(10)           C(11)-C(10)-Fe(1)-C(8)                             -156.97(14)           C(5)-C(1)-Fe(1)-C(10)                              -163.33(19)           C(2)-C(1)-Fe(1)-C(10)                               -45.0(3)           C(5)-C(1)-Fe(1)-C(4)                                -37.59(16)           C(2)-C(1)-Fe(1)-C(4)                                 80.70(17)           C(5)-C(1)-Fe(1)-C(2)                               -118.3(2)           C(2)-C(1)-Fe(1)-C(5)                                118.3(2)           C(5)-C(1)-Fe(1)-C(6)                                160.86(15)           C(2)-C(1)-Fe(1)-C(6)                                -80.85(16)           C(5)-C(1)-Fe(1)-C(3)                                -80.82(17)           C(2)-C(1)-Fe(1)-C(3)                                 37.47(15)           C(5)-C(1)-Fe(1)-C(9)                                 43.1(4)           C(2)-C(1)-Fe(1)-C(9)                                161.4(3)           C(5)-C(1)-Fe(1)-C(7)                                117.84(16)           C(2)-C(1)-Fe(1)-C(7)                               -123.87(14)           C(5)-C(1)-Fe(1)-C(8)                                 77.12(19)           C(2)-C(1)-Fe(1)-C(8)                               -164.59(13)           C(3)-C(4)-Fe(1)-C(10)                                71.70(17)           C(5)-C(4)-Fe(1)-C(10)                              -168.65(13)           C(3)-C(4)-Fe(1)-C(1)                                -81.62(17)           C(5)-C(4)-Fe(1)-C(1)                                 38.04(15)           C(3)-C(4)-Fe(1)-C(2)                                -37.21(15)           C(5)-C(4)-Fe(1)-C(2)                                 82.44(16)           C(3)-C(4)-Fe(1)-C(5)                               -119.7(2) 205            C(3)-C(4)-Fe(1)-C(6)                                 33.1(4)           C(5)-C(4)-Fe(1)-C(6)                                152.7(3)           C(5)-C(4)-Fe(1)-C(3)                                119.7(2)           C(3)-C(4)-Fe(1)-C(9)                                114.71(15)           C(5)-C(4)-Fe(1)-C(9)                               -125.64(15)           C(3)-C(4)-Fe(1)-C(7)                               -165.75(19)           C(5)-C(4)-Fe(1)-C(7)                                -46.1(3)           C(3)-C(4)-Fe(1)-C(8)                                157.44(13)           C(5)-C(4)-Fe(1)-C(8)                                -82.91(17)           C(3)-C(2)-Fe(1)-C(10)                               -82.53(15)           C(1)-C(2)-Fe(1)-C(10)                               158.94(14)           C(3)-C(2)-Fe(1)-C(1)                                118.5(2)           C(3)-C(2)-Fe(1)-C(4)                                 37.21(17)           C(1)-C(2)-Fe(1)-C(4)                                -81.32(18)           C(3)-C(2)-Fe(1)-C(5)                                 80.53(17)           C(1)-C(2)-Fe(1)-C(5)                                -38.00(17)           C(3)-C(2)-Fe(1)-C(6)                               -125.42(14)           C(1)-C(2)-Fe(1)-C(6)                                116.04(15)           C(1)-C(2)-Fe(1)-C(3)                               -118.5(2)           C(3)-C(2)-Fe(1)-C(9)                                -50.3(2)           C(1)-C(2)-Fe(1)-C(9)                               -168.88(18)           C(3)-C(2)-Fe(1)-C(7)                               -165.27(13)           C(1)-C(2)-Fe(1)-C(7)                                 76.20(17)           C(3)-C(2)-Fe(1)-C(8)                                167.6(2)           C(1)-C(2)-Fe(1)-C(8)                                 49.1(3)           C(4)-C(5)-Fe(1)-C(10)                                34.3(4)           C(1)-C(5)-Fe(1)-C(10)                               153.0(3)           C(4)-C(5)-Fe(1)-C(1)                               -118.6(2)           C(1)-C(5)-Fe(1)-C(4)                                118.6(2)           C(4)-C(5)-Fe(1)-C(2)                                -80.26(16)           C(1)-C(5)-Fe(1)-C(2)                                 38.37(15)           C(4)-C(5)-Fe(1)-C(6)                               -160.89(18)           C(1)-C(5)-Fe(1)-C(6)                                -42.3(3)           C(4)-C(5)-Fe(1)-C(3)                                -37.08(15)           C(1)-C(5)-Fe(1)-C(3)                                 81.55(16)           C(4)-C(5)-Fe(1)-C(9)                                 74.73(17)           C(1)-C(5)-Fe(1)-C(9)                               -166.64(13)           C(4)-C(5)-Fe(1)-C(7)                                160.34(14)           C(1)-C(5)-Fe(1)-C(7)                                -81.03(16)           C(4)-C(5)-Fe(1)-C(8)                                117.06(15)           C(1)-C(5)-Fe(1)-C(8)                               -124.32(14)           C(7)-C(6)-Fe(1)-C(10)                               118.64(14)           C(7)-C(6)-Fe(1)-C(1)                                -84.77(13)           C(10)-C(6)-Fe(1)-C(1)                               156.58(11)           C(7)-C(6)-Fe(1)-C(4)                                168.6(3)           C(10)-C(6)-Fe(1)-C(4)                                50.0(3)           C(7)-C(6)-Fe(1)-C(2)                               -126.91(12)           C(10)-C(6)-Fe(1)-C(2)                               114.45(11)           C(7)-C(6)-Fe(1)-C(5)                                -54.9(2)           C(10)-C(6)-Fe(1)-C(5)                              -173.54(18)           C(7)-C(6)-Fe(1)-C(3)                               -166.24(12)           C(10)-C(6)-Fe(1)-C(3)                                75.12(13)           C(7)-C(6)-Fe(1)-C(9)                                 80.48(11)           C(10)-C(6)-Fe(1)-C(9)                               -38.17(9)           C(10)-C(6)-Fe(1)-C(7)                              -118.64(14)           C(7)-C(6)-Fe(1)-C(8)                                 37.03(11)           C(10)-C(6)-Fe(1)-C(8)                               -81.61(10) 206            C(4)-C(3)-Fe(1)-C(10)                              -126.58(17)           C(2)-C(3)-Fe(1)-C(10)                               113.97(13)           C(4)-C(3)-Fe(1)-C(1)                                 81.07(19)           C(2)-C(3)-Fe(1)-C(1)                                -38.38(14)           C(2)-C(3)-Fe(1)-C(4)                               -119.5(2)           C(4)-C(3)-Fe(1)-C(2)                                119.5(2)           C(4)-C(3)-Fe(1)-C(5)                                 37.17(17)           C(2)-C(3)-Fe(1)-C(5)                                -82.29(16)           C(4)-C(3)-Fe(1)-C(6)                               -168.34(16)           C(2)-C(3)-Fe(1)-C(6)                                 72.21(15)           C(4)-C(3)-Fe(1)-C(9)                                -83.94(18)           C(2)-C(3)-Fe(1)-C(9)                                156.61(12)           C(4)-C(3)-Fe(1)-C(7)                                161.5(3)           C(2)-C(3)-Fe(1)-C(7)                                 42.1(3)           C(4)-C(3)-Fe(1)-C(8)                                -52.1(3)           C(2)-C(3)-Fe(1)-C(8)                               -171.57(17)           C(8)-C(9)-Fe(1)-C(10)                              -119.00(14)           C(8)-C(9)-Fe(1)-C(1)                                 43.3(4)           C(10)-C(9)-Fe(1)-C(1)                               162.3(3)           C(8)-C(9)-Fe(1)-C(4)                                118.14(14)           C(10)-C(9)-Fe(1)-C(4)                              -122.86(14)           C(8)-C(9)-Fe(1)-C(2)                               -164.61(18)           C(10)-C(9)-Fe(1)-C(2)                               -45.6(2)           C(8)-C(9)-Fe(1)-C(5)                                 77.18(16)           C(10)-C(9)-Fe(1)-C(5)                              -163.82(14)           C(8)-C(9)-Fe(1)-C(6)                                -80.69(11)           C(10)-C(9)-Fe(1)-C(6)                                38.31(9)           C(8)-C(9)-Fe(1)-C(3)                                160.54(12)           C(10)-C(9)-Fe(1)-C(3)                               -80.47(13)           C(8)-C(9)-Fe(1)-C(7)                                -37.02(10)           C(10)-C(9)-Fe(1)-C(7)                                81.98(10)           C(10)-C(9)-Fe(1)-C(8)                               119.00(14)           C(8)-C(7)-Fe(1)-C(10)                                81.52(11)           C(6)-C(7)-Fe(1)-C(10)                               -38.48(10)           C(8)-C(7)-Fe(1)-C(1)                               -126.67(12)           C(6)-C(7)-Fe(1)-C(1)                                113.33(12)           C(8)-C(7)-Fe(1)-C(4)                                -51.3(3)           C(6)-C(7)-Fe(1)-C(4)                               -171.3(2)           C(8)-C(7)-Fe(1)-C(2)                               -168.63(11)           C(6)-C(7)-Fe(1)-C(2)                                 71.37(13)           C(8)-C(7)-Fe(1)-C(5)                                -84.25(14)           C(6)-C(7)-Fe(1)-C(5)                                155.75(13)           C(8)-C(7)-Fe(1)-C(6)                                120.00(15)           C(8)-C(7)-Fe(1)-C(3)                                159.5(2)           C(6)-C(7)-Fe(1)-C(3)                                 39.5(3)           C(8)-C(7)-Fe(1)-C(9)                                 37.11(10)           C(6)-C(7)-Fe(1)-C(9)                                -82.89(11)           C(6)-C(7)-Fe(1)-C(8)                               -120.00(15)           C(7)-C(8)-Fe(1)-C(10)                               -81.88(11)           C(9)-C(8)-Fe(1)-C(10)                                38.22(9)           C(7)-C(8)-Fe(1)-C(1)                                 73.33(15)           C(9)-C(8)-Fe(1)-C(1)                               -166.57(13)           C(7)-C(8)-Fe(1)-C(4)                                158.42(15)           C(9)-C(8)-Fe(1)-C(4)                                -81.48(16)           C(7)-C(8)-Fe(1)-C(2)                                 34.9(3)           C(9)-C(8)-Fe(1)-C(2)                                155.0(3)           C(7)-C(8)-Fe(1)-C(5)                                115.67(15) 207            C(9)-C(8)-Fe(1)-C(5)                               -124.22(14)           C(7)-C(8)-Fe(1)-C(6)                                -37.29(10)           C(9)-C(8)-Fe(1)-C(6)                                 82.81(10)           C(7)-C(8)-Fe(1)-C(3)                               -164.7(2)           C(9)-C(8)-Fe(1)-C(3)                                -44.6(2)           C(7)-C(8)-Fe(1)-C(9)                               -120.10(14)           C(9)-C(8)-Fe(1)-C(7)                                120.10(14)           O(6)-C(21)-Co(1)-C(20)                              102.0(18)           O(6)-C(21)-Co(1)-C(22)                             -149.8(18)           O(6)-C(21)-Co(1)-C(13)                               -5.4(18)           O(6)-C(21)-Co(1)-C(14)                              -45.8(18)           O(6)-C(21)-Co(1)-Co(2)                              -18.6(18)           O(5)-C(20)-Co(1)-C(21)                              -97(7)           O(5)-C(20)-Co(1)-C(22)                              156(7)           O(5)-C(20)-Co(1)-C(13)                                2(7)           O(5)-C(20)-Co(1)-C(14)                               21(8)           O(5)-C(20)-Co(1)-Co(2)                               54(7)           O(7)-C(22)-Co(1)-C(21)                              132(4)           O(7)-C(22)-Co(1)-C(20)                             -126(4)           O(7)-C(22)-Co(1)-C(13)                               15(4)           O(7)-C(22)-Co(1)-C(14)                               29(4)           O(7)-C(22)-Co(1)-Co(2)                              -22(4)           C(14)-C(13)-Co(1)-C(21)                             -97.49(11)           C(12)-C(13)-Co(1)-C(21)                              50.31(17)           Co(2)-C(13)-Co(1)-C(21)                            -170.39(6)           C(14)-C(13)-Co(1)-C(20)                             162.83(10)           C(12)-C(13)-Co(1)-C(20)                             -49.37(18)           Co(2)-C(13)-Co(1)-C(20)                              89.93(7)           C(14)-C(13)-Co(1)-C(22)                              22.46(16)           C(12)-C(13)-Co(1)-C(22)                             170.26(16)           Co(2)-C(13)-Co(1)-C(22)                             -50.43(13)           C(12)-C(13)-Co(1)-C(14)                             147.8(2)           Co(2)-C(13)-Co(1)-C(14)                             -72.89(9)           C(14)-C(13)-Co(1)-Co(2)                              72.89(9)           C(12)-C(13)-Co(1)-Co(2)                            -139.31(19)           C(13)-C(14)-Co(1)-C(21)                              88.32(11)           C(15)-C(14)-Co(1)-C(21)                             -56.51(16)           Co(2)-C(14)-Co(1)-C(21)                             160.44(6)           C(13)-C(14)-Co(1)-C(20)                             -28.59(16)           C(15)-C(14)-Co(1)-C(20)                            -173.43(14)           Co(2)-C(14)-Co(1)-C(20)                              43.53(13)           C(13)-C(14)-Co(1)-C(22)                            -165.29(11)           C(15)-C(14)-Co(1)-C(22)                              49.88(17)           Co(2)-C(14)-Co(1)-C(22)                             -93.17(7)           C(15)-C(14)-Co(1)-C(13)                            -144.8(2)           Co(2)-C(14)-Co(1)-C(13)                              72.12(9)           C(13)-C(14)-Co(1)-Co(2)                             -72.12(9)           C(15)-C(14)-Co(1)-Co(2)                             143.05(18)           O(9)-C(24)-Co(2)-C(23)                             -101(4)           O(9)-C(24)-Co(2)-C(25)                              150(4)           O(9)-C(24)-Co(2)-C(13)                                1(4)           O(9)-C(24)-Co(2)-C(14)                               42(4)           O(9)-C(24)-Co(2)-Co(1)                               19(4)           O(8)-C(23)-Co(2)-C(24)                              132(2)           O(8)-C(23)-Co(2)-C(25)                             -122(2)           O(8)-C(23)-Co(2)-C(13)                               32(2)           O(8)-C(23)-Co(2)-C(14)                               14(2) 208            O(8)-C(23)-Co(2)-Co(1)                              -19(2)           O(10)-C(25)-Co(2)-C(24)                             166(100)           O(10)-C(25)-Co(2)-C(23)                              60(25)           O(10)-C(25)-Co(2)-C(13)                             -74(25)           O(10)-C(25)-Co(2)-C(14)                             -91(25)           O(10)-C(25)-Co(2)-Co(1)                             -39(25)           C(14)-C(13)-Co(2)-C(24)                              94.61(11)           C(12)-C(13)-Co(2)-C(24)                             -50.32(15)           Co(1)-C(13)-Co(2)-C(24)                             167.31(7)           C(14)-C(13)-Co(2)-C(23)                            -161.79(10)           C(12)-C(13)-Co(2)-C(23)                              53.28(15)           Co(1)-C(13)-Co(2)-C(23)                             -89.10(7)           C(14)-C(13)-Co(2)-C(25)                             -26.11(17)           C(12)-C(13)-Co(2)-C(25)                            -171.04(14)           Co(1)-C(13)-Co(2)-C(25)                              46.58(14)           C(12)-C(13)-Co(2)-C(14)                            -144.93(19)           Co(1)-C(13)-Co(2)-C(14)                              72.69(9)           C(14)-C(13)-Co(2)-Co(1)                             -72.69(9)           C(12)-C(13)-Co(2)-Co(1)                             142.38(16)           C(13)-C(14)-Co(2)-C(24)                             -91.54(11)           C(15)-C(14)-Co(2)-C(24)                              53.40(17)           Co(1)-C(14)-Co(2)-C(24)                            -163.82(7)           C(13)-C(14)-Co(2)-C(23)                              27.21(15)           C(15)-C(14)-Co(2)-C(23)                             172.15(14)           Co(1)-C(14)-Co(2)-C(23)                             -45.08(12)           C(13)-C(14)-Co(2)-C(25)                             164.17(10)           C(15)-C(14)-Co(2)-C(25)                             -50.89(17)           Co(1)-C(14)-Co(2)-C(25)                              91.88(7)           C(15)-C(14)-Co(2)-C(13)                             144.9(2)           Co(1)-C(14)-Co(2)-C(13)                             -72.29(9)           C(13)-C(14)-Co(2)-Co(1)                              72.29(9)           C(15)-C(14)-Co(2)-Co(1)                            -142.77(18)           C(21)-Co(1)-Co(2)-C(24)                              -6.00(15)           C(20)-Co(1)-Co(2)-C(24)                            -125.81(13)           C(22)-Co(1)-Co(2)-C(24)                             126.27(13)           C(13)-Co(1)-Co(2)-C(24)                             -23.08(13)           C(14)-Co(1)-Co(2)-C(24)                              29.71(13)           C(21)-Co(1)-Co(2)-C(23)                             115.70(11)           C(20)-Co(1)-Co(2)-C(23)                              -4.10(7)           C(22)-Co(1)-Co(2)-C(23)                            -112.03(8)           C(13)-Co(1)-Co(2)-C(23)                              98.63(8)           C(14)-Co(1)-Co(2)-C(23)                             151.42(8)           C(21)-Co(1)-Co(2)-C(25)                            -136.68(12)           C(20)-Co(1)-Co(2)-C(25)                             103.52(8)           C(22)-Co(1)-Co(2)-C(25)                              -4.41(8)           C(13)-Co(1)-Co(2)-C(25)                            -153.75(9)           C(14)-Co(1)-Co(2)-C(25)                            -100.96(8)           C(21)-Co(1)-Co(2)-C(13)                              17.07(11)           C(20)-Co(1)-Co(2)-C(13)                            -102.73(8)           C(22)-Co(1)-Co(2)-C(13)                             149.34(8)           C(14)-Co(1)-Co(2)-C(13)                              52.79(8)           C(21)-Co(1)-Co(2)-C(14)                             -35.71(11)           C(20)-Co(1)-Co(2)-C(14)                            -155.51(8)           C(22)-Co(1)-Co(2)-C(14)                              96.56(8)           C(13)-Co(1)-Co(2)-C(14)                             -52.79(8)          ________________________________________________________________  

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