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Coordination chemistry : basics to bioactive molecules Setyawati, Ika Agustin 1999

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COORDINATION CHEMISTRY: BASICS TO BIOACTIVE MOLECULES by  Ika Agustin Setyawati  B.Sc. (Hons.), The University of British Columbia, 1994  A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE STUDIES (Department of Chemistry)  We accept this thesis as conforming to the required standard  THE UNIVERSITY cMRITISH COLUMBIA July 1999 © Ika Agustin Setyawati  In presenting  this  thesis  in partial fulfilment  of  the  requirements  for  an advanced  degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department  or  by  his  or  her  representatives.  It  is  understood  that  copying  or  publication of this thesis for financial gain shall not be allowed without my written permission.  Department of  CHeMfeTR.^  The University of British Columbia Vancouver, Canada Date  DE-6 (2/88)  0^7  SO , 9 9 9 (  •  ABSTRACT  The stability constants of bis(maltolato)oxovanadium(IV) (BMOV, or VO(ma)2) and bis(kojato)oxovanadium(IV) (BKOV, or VO(ka) ) at 25 °C (0.15 M NaCl) were measured. 2  The former was found to be slightly more stable that the latter system. Since BMOV exhibits favourable chemical and insulin-enhancing properties in streptozotocin(STZ)-diabetic rats, the biodistributions of BMOV and its parent compound, vanadyl sulfate  (VOSO4  or VS),  using V as a tracer via oral or intraperitoneal administration in rats were studied. The data 4 8  were analyzed using compartmental modeling. The results showed that tissue uptake of V 48  from an oral dose of V-BMOV was approximately two to three times greater than that from 48  an equivalent dose of VS. This is consistent with previous studies in which a two to three 48  times increased acute glucose-lowering potency was seen with BMOV compared with VS. The reactions of potentially hexadentate H^bbpen (N,N'-bis(2-hydroxybenzyl)-N,N'bis(2-methylpyridyl)ethylenediamine,  H2LI),  H^Clbbpen  (N,N'-bis(5-chloro-2-  hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine, H2L2), and H^Brbbpen (N,N'bis(5-bromo-2-hydroxybenzyl)-N,N' -bis(2-methylpyridyl)ethylenediamine,  H2L3)  with  Ln(III) ions in the presence of a base in methanol resulted in three types of complex: neutral mononuclear ([LnL(N03)]), monocationic dinuclear ([Ln2L2(N03)] ) and monocationic +  trinuclear ([Ln L2(X)n(CH OH)] ), where X = bridging (CH3COO") and bidentate ligands +  3  3  (NO3", CH3COO", or CIO4") and n is 4. The formation of a complex depends on the base (hydroxide or acetate) and the size of the respective Ln(III) ion. All complexes were characterized by infrared spectroscopy, mass spectrometry, elemental analyses, and in some cases, by X-ray diffraction studies. The [LnL(N0 )] or [Ln2L (N03)] complexes can be +  3  2  converted to [Ln3L2(X) (CH30H)] complexes by addition of one equivalent of a Ln(III) salt, +  n  and 2-3 equivalents of sodium acetate in methanol. The trinuclear complexes were found to be surprisingly stable, evinced by the presence of the intact monocationic high molecular weight parent peaks ([Ln3L2(X) ] ) in the mass spectra of all trinuclear complexes, and from +  n  the ease of conversion from the mononuclear or dinuclear to the trinuclear species. X-ray crystal structures showed myriad modes of coordination geometry around Ln(III). The incompatibility of the ligand denticity with the coordination requirements of the Ln(III) ions was proven to be a useful tool in the construction of multinuclear Ln(III) metal ion arrays. The complexation of Fe and [Re O] with bbpen" (LI ") and Clbbpen" (L2") 3+  v  3+  2  2  2  2  resulted in the formation of monocationic complexes. The X-ray crystal structure of distorted octahedral [Fe(Ll)]N03»CH30H showed the same coordination environment as in its previously studied Ga(III) and In(III) congeners. The solid state and solution structures of a monocationic oxorhenium(V) complex with H2LI ([ReO(Ll)] ) were quite symmetric, with +  a pentagonal bipyramidal geometry.  - iii -  TABLE OF CONTENTS  Abstract  ii  Table of Contents  iv  Lists of Figures  vii  Lists of Tables  xi  Lists of Abbreviations  xiv  Acknowledgments  xx  Dedication  xxi  Chapter 1  Chapter 2  General Introduction  1  References  5  Stability Constant Determinations of Vanadium(IV) Complexes, and Biodistribution Studies of V-labeled 48  Vanadyl Sulfate and Bis(maltolato)oxovanadium(IV) 2.1.  Introduction  6  2.2.  Experimental  12  2.3.  Results and Discussion 2.3.1. Stability constant determinations of  19  vanadium(IV) complexes 2.3.2. Biodistribution studies of V-labeled 48  24  vanadyl sulfate (VS) and BMOV 2.4.  References  35  - iv -  Chapter 3  Lanthanide(III) Complexes with Hexadentate Aminopyridylphenolate Ligands  Chapter 4  3.1.  Introduction  40  3.2.  Experimental  46  3.3.  Results and Discussion  3.4.  References  50 83  Iron(III) Complex with a Hexadentate Aminopyridylphenolate Ligand  Chapter 5  4.1.  Introduction  87  4.2.  Experimental  89  4.3.  Results and Discussion  4.4.  References  90 100  Oxorhenium(V) Complexes with Hexadentate Aminopyridylphenolate Ligands  Chapter 6  5.1.  Introduction  103  5.2.  Experimental  105  5.3.  Results and Discussion  5.4.  References  106 115  Conclusions and Further Thoughts 6.1.  General Conclusions  6.2.  Suggestions for Future Work  120  6.3.  Preparation of H N 02 (l,7-bis(2-hydroxybenzyl)-  123  2  118  6  1,4,7-tris(2-methylpyridyl)-1,4,7-triazaheptane)  - v-  6.4. Appendices  References  Lists of Figures  Figure  Description  Page  1.1.  Bis(maltolato)oxovanadium(IV), BMOV and  4  bis(kojato)oxovanadium(IV), BKOV. 1.2.  Hexadentate pro-ligands discussed in Chapters 3 and 4.  2.1.  Speciation diagram of V(V) as a function of pH.  4 7  Total vanadium concentration is equal to 10 pM. 2.2.  VO(0 )(pic)»2H 0  8  2.3.  Speciation diagram ofV(IV) as a function of pH.  8  2  2  Total vanadium concentration is equal to 10 pM. 2.4.  Variable pH (2-3) UV-spectra of VO(ma) (k= 250-360 nm) and +  21  experimental (points)/calculated (lines) absorbances vs pH (inset). TheL:Mratiois0.11. 2.5.  Titration curves as a plot of n vs the log of free ligand concentration  22  for L:M ratios ranging from 0.17 to 10 for both the V0 /Hma 2+  and V0 /Hka systems. 2+  2.6.  Speciation diagram for the V0 /Hma system (1 mM V0 , 2 mM Hma).  22  2.7.  Speciation diagram for the V0 /Hka system (1 mM V0 , 2 mM Hka).  23  2.8.  Average tissue distributions of V in rats (n=3 for each time point) after  25  2+  2+  2+  2+  48  administration of V-BMOV (A and C) or VS (B and D) by oral gavage. 48  48  2.9.  Compartmental model of vanadium metabolism.  2.10.  Calculated (dashed or solid lines) and observed (points) decay curves  - vii -  26 28  after oral (top) and i.p. (bottom) administration of V-BMOV (A) 48  or VS (B). 48  3.1.  IR bands (1520-1200 cm") of all mononuclear [LnL(N0 )]  53  1  3  (Ln=Dy-Lu) and dinuclear [Ln2L2(N03)]N03 (Ln=La-Gd) complexes. t, bidentate nitrate stretching bands; 8, C - 0 deformation bands of bridging phenolate; •, free (uncoordinated) nitrate stretching bands. 3.2.  Mass spectrum of trinuclear [Gd (Ll)2(CH3COO)2(N03)2(CH30H)]N0  3  3  57  showing the experimental (lower) and simulated (upper) isotopic patterns for major peaks. 3.3.  ORTEP diagram of [Yb(Ll)] NO3 and a scheme of the coordination  61  geometry around Yb(III), shown with the same numbering as the crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 3 3 % probability level. 3.4.  ORTEP diagram of the [Pr (Ll)2(N03)(H 0)] cation in 2  2  +  64  [Pr (Ll)2(N03)(H20)]N03»CH OH and a scheme of the coordination 2  3  geometries around each Pr(III) center, shown with the same numbering as the crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 3 3 % probability level and some of the phenolate and pyridyl ring atoms have been omitted for clarity. 3.5.  ORTEP diagram of the [Gd (Ll)2(N0 )] cation in 3  2  +  [Gd (Ll)2(N03)]N03«CH OH«3H20 and a scheme of the coordination 2  3  geometries around each Gd(III) center, shown with the same numbering as the crystallographic numbering. Thermal ellipsoids for the non-  - viii -  68  hydrogen atoms are drawn at the 33% probability level and some of the phenolate and pyridyl ring atoms have been omitted for clarity. 3.6.  ORTEP diagram of the [Gd (L3)2(CH COO)4(CH30H)] cation in +  3  3  72  [Gd(L3)2(CH3COO)4(CHOH)] C10 »5CH OH and a scheme of the 3  3  4  3  coordination geometries around each Gd(III) center, shown with the same numbering as the crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 33% probability level and some of the phenolate and pyridyl ring atoms have been omitted for clarity. 3.7.  ORTEP diagram of the [Sm (Ll) (CH COO)2(N03) (CH OH)] cation in +  3  2  3  2  3  77  [Sm (Ll)2(CH COO)2(N0 )2(CH OH)] N0 »CH Orh»3.65H 0 and a 3  3  3  3  3  3  2  scheme of the coordination geometry around Sm(2), shown with the same numbering as the crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 33% probability level and some of the phenolate and pyridyl ring atoms have been omitted for clarity. 4.1.  ORTEP drawing of the [Fe(Ll)] cation in [Fe(Ll)] N0 »CH OH showing +  3  3  92  the crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 33% probability level. 4.2.  UV/visible spectrum of 62 pM [Fe(Ll)]N03 in acetonitrile.  95  4.3.  Qualitative energy level diagram showing the effect of ligand phenolate  97  prc-orbital interaction with d-orbitals of iron(III). 4.4.  Cyclic voltammogram of [Fe(Ll)]N0 in CH CN 3  98  3  (0.25 M (TBA)PF ), scan rate is 100 mV/s. 6  5.1.  ORTEP drawing of the [ReO(Ll)] cation in [ReO(Ll)]PF +  6  - IX •  108  showing the crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 3 3 % probability level. 5.2.  !  H NMR spectra of pro-ligand H L1 in DMSO-cfc (top), and 2  111  of [ReO(Ll)]PF6 in acetone-^ (bottom). 5.3.  The'H-^ COSY spectrum of [ReO(Ll)]PF in acetone-^. 6  - X -  112  Lists of Tables  Table  Description  Page  2.1.  Deprotonation Constants (pK 's) and Stability Constants of V O L 2 .  20  2.2.  Relative Concentrations of V 24 h after Oral Gavage (% AD/g tissue).  29  2.3.  Fractional Transfer Coefficients between Compartments of V  31  a  48  48  Model (h"), and Residence Times of V in Key Compartments. 1  48  3.1.  Effective Ionic Radii ofLn(III) Ions (A).  41  3.2.  Preparative Details for the Trinuclear ([Ln L2(X)n(CH OH)]Y) Complexes.  48  3.3.  Infrared Spectral Data of Nitrates, Acetates and Bridging Phenolates  55  3  3  (cm", KBr disk) in the Lanthanide Complexes. 1  3.4.  LSIMS Data for the Lanthanide Complexes (+ mode).  58  3.5.  Analytical Data [Calcd(found)] and Room Temperature Magnetic Moments  59  for the Lanthanide Complexes. 3.6.  Selected Bond Lengths (A) and Bond Angles (deg) in [Yb(L 1 )N0 ].  62  3.7.  Selected Bond Lengths (A) and Bond Angles (deg) in the Cation of  65  3  [Pr (Ll) (N03)(H 0)] [N0 ].CH OH. 2  3.8.  2  2  3  3  Selected Bond Lengths (A) and Bond Angles (deg) in the Cation of  69  [Gd2(Ll) (N0 )][N0 ]»CH OH»3H 0. 2  3.9.  3  3  3  2  Selected Bond Lengths (A) and Bond Angles (deg) in the Cation of  74  [Gd (L3) (CH COO) (CH OH)][ClO ]*0.5CH OH. 3  3.10.  2  3  4  3  4  3  Selected Bond Lengths (A) and Bond Angles (deg) in the Cation of [Sm (Ll) (CH COO) (N0 ) (CH OH)][N03]«CH OH«3.65H 0. 3  2  3  2  3  2  3  - xi -  3  2  79  4.1.  Selected Bond Lengths (A) and Bond Angles (deg) in the cation of  93  [Fe(Ll)]N0 *CH OH. 3  5.1.  3  Selected Bond Lengths (A) and Bond Angles (deg) in the cation of  109  [ReO(Ll)]PF . 6  5.2.  'H NMR Data (200 MHz) for the Re(V) Complexes in acetone-cfc.  Al.  Biodistribution of V-BMOV Oral Administration in Rats.  113 126  48  (Experiment A - n=3, %AD/gram organ, mean (SD)) A2.  Biodistribution of VS Oral Administration in Rats.  127  48  (Experiment A - n=3, %AD/gram organ, mean (SD)) A3.  Biodistribution of V-BMOV Oral Administration in Rats.  128  48  (Experiment B - n=3, %AD/gram organ, mean (SD)) A4.  Biodistribution of VS Oral Administration in Rats.  129  48  (Experiment B - n=3, %AD/gram organ, mean (SD)) A5.  Biodistribution of V-BMOV i.p. Administration in Rats.  130  48  (Experiment C - n=3, %AD/gram organ, mean (SD)) A6.  Biodistribution of VS i.p. Administration in Rats.  130  48  (Experiment C - n=3, %AD/gram organ, mean (SD)) A7.  Selected Crystallographic Data for the Mononuclear, Dinuclear  131  and Trinuclear Ln(III) Complexes. A8.  Bond Lengths (A) and Bond Angles (deg) for [Yb(Ll)N0 ].  132  A9.  Bond Lengths (A) and Bond Angles (deg) for  134  3  [Pr (Ll) (N0 )(H 0)][N0 ]'CH OH. 2  2  3  2  3  3  - xii -  A10.  Bond Lengths (A) and Bond Angles (deg) for  138  [Gd (Ll)2(N03)][N03]»CH OH'3H20. 2  All.  3  Bond Lengths (A) and Bond Angles (deg) for  142  [Gd3(L3) (CH3COO)4(CH3OH)][ClO4]«0.5CH OH. 2  A12.  3  Bond Lengths (A) and Bond Angles (deg) for  147  [Sm3(Ll) (CH3COO) (N03) (CH30H)][N03]'CH OH»3.65H 0. 2  2  2  3  2  A13.  Selected Crystallographic Data for [Fe(L 1 )]N0 «CH OH.  A14.  Bond Lengths (A) and Bond Angles (deg) for [Fe(Ll)]N0 «CH OH.  153  A15.  Selected Crystallographic Data for [ReO(Ll)]PF .  155  A16.  Bond Lengths (A) and Bond Angles (deg) for [ReO(Ll)]PF .  3  152  3  3  3  6  6  - xiii -  156  List of Abbreviations  Abbreviation Meaning ~  approximate  A  angstrom, 1 x 10" metre  Abs  absorbance  AD  adminstered dose  Anal  analytical  ATPase  adenosine triphosphatase  avg  average  P  beta particles  p  10  overall stability constant of n stepwise equilibria  n  bdmapH  1,3 -bis(dimethylamino)-2-propanol  bdmmpH  2,6-bis[(dimethylamino)methyl]-4-methylphenol  BKOV  bis(kojato)oxovanadium(IV)  BM  Bohr magneton  BMOV  bis(maltolato)oxovanadium(IV)  br  broad (IR)  Cx  total concentration of species X  calcd  calculated  °C  degrees Celcius  Ci  curie  cm"  1  wavenumber(s) (reciprocal centimeter)  - xiv -  COSY  correlated spectroscopy (NMR)  cryst  crystal  CV  coefficients of variation  5  deformation band (IR); chemical shift in parts per million (ppm) from tetramethylsilane (NMR)  d  day(s); doublet (NMR)  dd  doublet of doublets (NMR)  deg  degree  dien  diethylenetriamine  DMSO  dimethylsulfoxide  D03 A  1,4,7-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecane  DTPA  N,N,N',N",N"'-diethylenetriaminepentaacetic acid  s  extinction coefficient (UV) in M^cm"  E1/2  half-point between oxidation and reduction potentials in electrochemistry  1  EDDHA "  ethylenediamine di(o-hydroxyphenylacetate) •  en  ethylenediamine  4  AE  P  the difference between oxidation and reduction potentials in electrochemistry  eV  electron volt(s)  FT  fourier transform  fw  formula weight  y  gamma rays  g  gram(s)  - XV -  GI  gastrointestinal  h  hour(s)  H apa  N,N'-3-azapentane-l,5-diylbis(3-(l-iminoethyl)-6-methyl-2H-pyran-2-4-  3  (3H)-dione H2bad  1,10-bis(2-hydroxyphenyl)-1,4,7,10-tetraazadecane  Habben  N,N' -bis(2-hydroxybenzyl)ethylenediamine  H2bbpen  N,N'-bis(2-hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine,  H L1 2  H bhpmp 3  2,6-bis[((2-hydroxybenzyl)(2-pyridylmethyl)amino0methyl]-4methylphenol)  H bhpp  1,3-bis[(2-hydroxybenzyl)(2-pyridylmethyl)amino]-2-propanol)  H2bpdien  1,7-bis(2-hydroxybenzyl)-1,4,7-triazaheptane  3  H2bped  bis-(2-pyridylmethyl)ethylenediamine-N,N'-diacetic acid  H Brbbpen  N,N'-bis(5-bromo-2-hydroxybenzyl)-N,N'-bis(2-  2  methylpyridyl)ethylenediamine, H2L3  H Clbbpen 2  N,N'-bis(5-chloro-2-hydroxybenzyl)-N,N'-bis(2methylpyridyl)ethylenediamine, H2L2  HEDP  hydroxyethylidene diphosphonate  Hka  kojic acid, 5-hydroxy-2-hydroxymethyl-4-pyrone  Hma  maltol, 3-hydroxy-2-methyl-4-pyrone  HN0 2  6  2  1,7-bis(2-hydroxybenzyl)-1,4,7-tris(2-methylpyridyl)-1,4,7-triazaheptane  H pmen  N,N' -bis(2-methylpyridyl)ethylenediamine  tbsalen  N, N'-bis(salicylidene)ethylenediamine  2  - xvi -  Hz  hertz  IDDM  insulin dependent diabetes mellitus  Im  imidazole  i.p.  intraperitoneal  IR  infrared  i.v.  intravenous  J  total angular momentum of the ground state (pff calculation)  k  kilo- (10 )  ky  fractional transfer coefficient moving from compartment j to i (per unit  e  3  time) K  n  X  stepwise stability constant of the n-th equilibrium wavelength  A,ax  wavelength at peak maximum  L  litre; ligand  LMCT  ligand to metal charge transfer  Ln  lanthanides  LSIMS  liquid secondary ion mass spectrometry  p  micro- (10")  Peff  effective magnetic moment in BM  m  milli- (10"); medium (IR); multiplet (NMR)  M  molar (moles/litre for concentration); metal  MCF-7  a type of human breast cancer cell  1-Meim  1-methylimidazole  m  6  3  - xvii -  min  minute(s)  mpenOH  N-(2-pyridylmethyl)-2-aminoethanol  MRI  magnetic resonance imaging  m/z  mass to charge ratio (in mass spectrometry)  n  nano- (10"); number of samples  n  moles of bound ligand per mole of metal ion  v  stretching frequency (IR)  NIDDM  non-insulin dependent diabetes mellitus  NMR  nuclear magnetic resonance  OAc  acetate  ORTEP  Oak Ridge Thermal Ellipsoid Program  PC  personal computer  phen  phenanthroline  pH  negative log of the concentration of H (proton)  9  pK  +  a  negative log of the acid dissociation constant, K  a  pic  picolinate, pyridine-2-carboxylate  ppm  parts per million  pro-ligand  the organic molecule from which the ligand bound to the metal is derived  py  pyridyl  pi  calculated density  II  Residence Time (in compartmental analysis)  s  second(s); strong (IR); singlet (NMR)  a, SD  standard deviation  ca c  - xviii -  SCE  standard calomel electrode  SE  standard error (defined as SD/(n ), where n = number of samples)  STZ.  streptozotocin  syst  system  t  triplet (NMR)  ti/2  half-life  taci  l,3,5-triamino-l,3,5-trideoxy-c/,y-inositol  TBA  1/2  tetra-H-butylammonium  td  triplet of doublets (NMR)  TMS  tetramethylsilane (NMR)  tpen  N,N,N',N-tetrakis(2-methylpyridyl)ethylenediamine  transm  transmission  trien  triethylenetetramine  TRIUMF  Tri-University Meson Facility  V  volt(s)  V  volume  UV  ultraviolet  vis  visible  VS  vanadyl sulfate  Z  atomic number  Z  number of molecules per unit cell  ,  - xix -  ACKNOWLEDGMENTS  First and foremost, I must acknowledge Professor Chris Orvig for his continuous support, guidance, patience and enthusiasm. He gave me the freedom and independence in my scientific journey in the wonderful world of coordination chemistry of many elements. I also want to thank him for his constant encouragement and optimistic views when pessimistic thoughts completely overwhelmed me. I would like to thank Dr. Kathie Thompson, especially for sharing her knowledge in compartmental modeling and about vanadium in general, as well as Pete Caravan, Dr. Yan Sun, Violet Yuen, Dr. J. H. McNeill and Dr. Don Lyster for their collaboration in the vanadium project. A special acknowledgement is directed towards the late Dr. Steve Rettig; without his help in solving the crystal structures of the Ln-complexes, it would have been more difficult to characterize them. Acknowledgement is made to Dr. Victor Young at the University of Minnesota for the determination of the crystal structure of [ReO(Ll)]PF6. Thanks to Equipe Orvig Team, especially to Ernest, Marco, Leon, Jason, Lenny, Ashley, Paul, Grandpa Buglyo, Nico, Elisabetta and other past and present members of Orvig Group for their help, suggestions and for the nice memories of our group. The assistance of the departmental support staff (Ms. Liane Darge and Ms. Marietta Austria (NMR), Mr. Peter Borda (elemental analysis), Lina Madilao and Chris (mass spectrometry)) is gratefully acknowledged. NSERC, DuPont Pharmaceuticals, and the UBC Chemistry Department are thanked for financial support. Finally, I gratefully acknowledge my parents and sister for their never ending support, physically and mentally, during the course of my study. Thanks always to Dale for his patience and support.  - XX -  I dedicate this thesis to my parents, my sister and Dale with much love  - xxi -  CHAPTER 1  General Introduction  Nature incorporates many metallic elements in living systems. At least 10 out of 25 elements that are thought to be essential for warm-blooded mammals are metallic. Metal ions in biological systems, such as in proteins (so called metalloproteins), have been known to perform a variety of important tasks. An example of a metalloprotein is hemoglobin, an iron-containing protein, which is involved in oxygen binding and transport throughout body tissues. A subclass of metalloproteins is the metalloenzymes, metal-containing proteins that catalyze chemical reactions in living systems.  Manganese, iron, copper and zinc are  examples of metal ions found in metalloenzymes (for a comprehensive review see Chem. Rev. November 1996 issue).  1  Since metal ions are known to be important in the natural biological functions of living systems, the potential pharmacological roles of essential, and even of non-essential, metal ions are a logical subject to be explored. In fact, the application of inorganic compounds in medicine dates back to ancient times. The Egyptians were thought to have used copper to sterilize water in 3000 BC, and the Chinese used gold in medicine around 2500 BC. During the Renaissance period, mercurous chloride was known to be a diuretic. Despite their positive benefits, the compounds used in ancient times were not chemically well characterized or studied. It was not until the turn of this century that medicinal inorganic chemistry began to be developed in a rational manner. This work was initiated by Ehrlich's first structure-activity relationship study in the early 20 century involving the th  References on p. 5  Chapter 1  development of the inorganic arsenic compound, arsphenamine (also known as Salvasaran or Ehrlich 606), as a successful treatment of syphilis. In 1929, gold compounds were first used 2  by French physicians to treat rheumatoid arthritis; a practice which is still widespread today. Mercurial diuretics were still widely used until the 1950s. The biological mechanisms of those compounds were not well understood; presently, this is still true for many compounds. The common features possessed by the compounds mentioned above are that they are all coordination compounds. They contain metal ions bound to organic moieties (ligands). The structure-activity relationship is a fundamental concept in medicinal chemistry. It is mostly based on the development of organic moieties to alter the properties of metal complexes (for reviews see September 1999 issue of Chem. Rev.).  3  Over this century, the focus in the research on the use of inorganic compounds in medicine has been on the design of well-characterized compounds that will target specific organs and/or perform specific functions in the body. Ideally, such compounds should be relatively water soluble, kinetically inert to demetallation and/or thermodynamically stable toward hydrolysis, stable toward ligand exchange and demetallation by blood proteins, such as transferrin, under physiological conditions. They should also be lipophilic, relatively small in size and neutral in charge to be able to pass through cell membranes via passive diffusion. The redox properties of the central metal ion should also be of consideration under physiological conditions.  The accumulation and clearance of the compounds should be  sufficient to minimize toxicity in the body. To achieve these ideal properties, metal complexes and their characteristics can be adjusted by modification of their organic ligands. The overall charge and size of complexes can be tuned based on the charge and size of the ligands, respectively.  -2-  The solubility  References on p. 5  Chapter 1  depends on the overall charge and the concomitant lipophilicity or hydrophilicity. The stability under physiological conditions depends on the thermodynamic stability of the metal complex.  Multidentate ligands usually form thermodynamically more stable complexes  because of the chelate effect. As a general rule, complexes with one (or more) five and/or six membered chelate rings are more stable than similar complexes lacking such a ring. The chelate effect is essentially an entropic phenomenon.  4  Multidentate ligands usually form  complexes with slow ligand exchange kinetics because a step-wise process of breaking the bonds from the central metal ion to the ligands' donor atoms is required. Some examples of metal ions in biologically active coordination complexes investigated or used in medicine as therapeutic or diagnostic agents presently are rhenium (Re), technetium (Tc) and some lanthanide metal ions such as gadolinium (Gd) and samarium (Sm). Vanadium (V) is found to be biologically active as a potential insulin mimic in type II or non-insulin dependent diabetes mellitus (NIDDM). These metal ions are the focus of the projects presented in this thesis. This thesis will attempt to illustrate some of the relevant steps from the basic chemistry to biological testing in the development of potentially useful metal complexes in medicine.  First, the stability constant determinations of two vanadium coordination  complexes, bis(maltolato)oxovanadium(IV) (VO(ma)2) and bis(kojato)oxovanadium(IV) (VO(ka)2), abbreviated as BMOV and BKOV respectively, are reported in Chapter 2. Biodistribution studies of BMOV and of its parent compound, vanadyl sulfate (VOSO4), using radioactive V in rats are also included in Chapter 2. 48  References on p. 5  Chapter 1  O  CH  O  3  HO' OH CH  3  BKOV  BMOV Figure 1.1.  Bis(maltolato)oxovanadium(IV), BMOV and bis(kojato)oxovanadium(rV),  BKOV  Maltol (3-hydroxy-2-methyl-4-pyrone) is an approved food additive in both Canada and the U.S.A., and kojic acid (5-hydroxy-2-hydroxymethyl-4-pyrone) is a naturally occurring compound. Previous studies from our laboratory have shown that BMOV is orally more active in lowering plasma glucose levels in streptozotocin-diabetic rats (an experimental model of diabetes) than its parent compound, vanadyl sulfate, and is non-toxic over a six month period of administration.  5  In Chapter 3, the basic coordination chemistry of lanthanide metal ions (Ln(III)) with hexadentate pro-ligands (Figure 1.2) will be discussed. Chapters 4 and 5 cover the chemistry of the same pro-ligand system with iron(III) and oxorhenium(V), respectively. General conclusions and suggestions for future work are presented in Chapter 6.  Z = H, H bbpen = CI, H Clbpen = Br, H Brbpen 2  2  2  Figure 1.2. Hexadentate pro-ligands discussed in Chapters 3, 4 and 5.  -4-  References on p. 5  Chapter 1  References  1)  This special issue of Chem. Rev. 1996, 96, 2237 is dedicated to the topic of bioinorganic enzymology.  2)  Albert, A. Selective Toxicity; 7th ed.; Chapman and Hall: New York, 1985, p. 206-219.  3)  This special issue of Chem. Rev. 1999, 99 is dedicated to medicinal inorganic chemistry topics.  4)  Cotton, F. A.; Wilkinson, G.; Gaus, P. L. Basic Inorganic Chemistry, 3rd Ed.; John Wiley & Sons, Inc.: New York, 1995, p. 186-187.  5)  Yuen, V. G.; Orvig, C ; McNeill, J. H. Can. J. Physiol. Pharmacol. 1995, 73, 55.  CHAPTER 2  Stability Constant Determinations of Vanadium(IV) Complexes, and B i o d i s t r i b u t i o n Studies o f V - l a b e l l e d V a n a d y l S u l f a t e a n d 4 8  Bis(maltolato)oxovanadium(IV)  2.1. Introduction The first-row transition metal vanadium was first discovered by Nils Gabriel Sefstrom in 1831. He named it after Vanadis, the Norse goddess of beauty, because of its beautiful multicoloured compounds. The average concentration of vanadium in the earth's crust is 100 ppm, higher than those of copper, lead, zinc and tin in the crust. The 1  concentration of dissolved vanadium in sea water was found to be around 35 nM; ' thus, 2 3  some marine organisms accumulate vanadium in their systems. In fact, in the early 1900s high accumulation of vanadium wasfirstfound in ascidian blood cells. This element has 4  also been detected in the active site of haloperoxidase enzymes in a number of marine algae and lichens and in the active site of Azotobacter nitrogenases. Having a concentration less 5  6  than 0.1 pM in mammalian tissues, vanadium is an ultratrace element whose essentiality has 7  not yet been conclusively demonstrated. Homeostatic mechanisms ensure low levels of absorption of dietary vanadium and rapid clearance of vanadium from the bloodstream. 8  9  Vanadium's oxidation states range from -3 to +5. In biological systems, oxidation states of +3, +4 and +5 can be found, although the most prevalent forms are vanadyl (V0 , 10  2+  -6-  References on p. 35  Chapter 2  V(IV)) and vanadate (a general term describing V(V)). A V(V) speciation diagram as a function of pH is presented in Figure 2.1.  Figure 2.1.  Speciation diagram of V(V) as a function of pH.  11  Total vanadium  concentration is equal to 10 pM.  At a concentration below 10 pM, V 0  + 2  and H3VO4 are present at low pH, and at extremely  high pH (>12), the only most dominant species is VO4 ". Most mammalian tissues contain an intracellular vanadium concentration of 0.1-1.0 pM; thus, the most predominant species of 12  V(V) are monovanadate H3VO4, H V0 " and HVO4 (at pH 4-8). At high concentration of 2  2  4  V(V) (lOmM), polymeric forms of vanadate exist. The coordination chemistry of V(V) is dominated by VO  and cw-V0 moieties. 2  Vanadium(V)-containing bromoperoxidases, enzymes which catalyze the oxidation of Br" to Br by H 0 , are postulated to proceed through chemical reactions in which peroxide 2  2  2  coordinates to V(V). The majority of peroxovanadate complexes are seven coordinate with pentagonal bipyramidal geometry, such as that adapted by VO(0 )(pic)*2H 0.  13  2  -7-  2  References on p. 35  Chapter 2  O f"»..  H0 2  V. o  OH,  Figure 2.2. VO(0 )(pic>2H 0.  13  2  2  A similar geometry was also found in other peroxovanadate complexes involving nicotinate,  14  citrate, and oxalate ligands. 15  16  It is known that the structure of VO4" shows a remarkable resemblance to that of 3  phosphate anion (PO4") in size, geometry and even in function. Cantley et a/. 3  17  18  first  reported the function of vanadate as an inhibitor of Na -K -ATPase in vitro. Vanadate can +  +  easily form a stable trigonal bipyramidal geometry, and act as a phosphate transition state analog.  17  ) Sped  CO ',00 CD  Molle%  > >  1 . . vo  •  i.  > /  60  20 -  VO(OH)  \ /  2  V  O  (  O  H  )  3  -  VOOH v^^ +  40  \  (VOOH)^y 1;  j;  1 —-r 3  S  ^—TT < \ j S  18;  4  .. i--" 9  \ 1  10  — %  11  f 12  13  PH  Figure 2.3. Speciation diagram of V(IV) as a function of pH. Total vanadium concentration is equal to 10 pM.  19  -8-  References on p. 35  Chapter 2  A vanadium(rV) speciation diagram as a function of pH is shown in Figure 2.3. With a total vanadium concentration of 10 pM, the major species at low pH is V 0 , and 2+  hydrolyzed species dominate at higher pH. The latter species can be easily oxidized to V(V); however, chelation of the V 0  2+  core retards this process. Inside the cells, the reduction of  V(V) to V(rV) can proceed readily with glutathione as a reducing agent. The coordination chemistry of vanadium(rV) is mostly centered around the V 0  2+  core.  The general  coordination geometries around this core are octahedral, square pyramidal and trigonal bipyramidal. V(IV) complexes containing "bare" V(IV) ions (those lacking coordinated 20  oxide ligand) were once considered to be rare, but more examples of these complexes have been found since Stiefel et al. reported a dianonic complex of tris(l,2-dicyanoethylene-l,221  dithiolato) with V(IV), the first non-oxo V(IV) complex. Physiological effects of vanadium were studied as early as the late 19 century, th  including therapeutic applications of vanadium in the treatment of diabetes in France.  22  Presently, diabetes mellitus affects millions of people in North America. Two types of diabetes mellitus are known: type I (previously known as insulin-dependent diabetes mellitus, IDDM) and type II (previously known as noninsulin-dependent diabetes mellitus, NIDDM).  Type I is characterized by hypoinsulinemia because the pancreas no longer  produces enough insulin. Type II is characterized by hyperinsulinemia because the pancreas is still able to produce insulin but the body is no longer able to utilize it properly. Over the past decade, numerous laboratories have reported on the insulin-mimetic properties of vanadate and vanadyl both in vitro and in vivo. '  23 26  Among vanadium's most significant in  vitro effects in isolated tissues are increased glucose uptake and stimulation of glycogen synthesis in rat diaphragm, liver and fat cells, and enhanced glucose transport and oxidation 27  -9-  References on p. 35  Chapter 2  in rat adipocytes and skeletal muscle, of lipogenesis in rat adipocytes.  32  28-30  as well as inhibition of lipolysis, and activation 31  Because type II diabetes is characterized at least initially  by hyperinsulinemia and insulin resistance, not insulin deficiency, it is highly significant that vanadium stimulates glucose metabolism without increasing the circulating concentration of insulin. Since insulin is not active orally, this has catalyzed great interest in the possible therapeutic value of vanadium as an orally active agent against diabetes mellitus. In 1985, in vivo insulin-mimetic effects of vanadate were first reported in the streptozotocin (STZ) diabetic rat; however, vanadate is poorly absorbed from the gastrointestinal (Gl) tract into 33  the blood, and the necessary dosage is close to the toxic level.  34  Subsequently, vanadyl  sulfate (VS) has proven to be very promising, but it too is poorly absorbed. ' It is evident 23 26  that manipulation of the chemical form of vanadium is needed to increase Gl absorption and to reduce dosage to a non-toxic level. Several attempts to modify the biological uptake of vanadium by changing the chemical forms of either vanadate '  23 35-39  or vanadyl " 40  42  have been reported.  Diperoxovanadate chelate complexes were found very active in vitro,  29  but no oral  administration data have been reported. Vanadyl complexes reported above either had poor stability in water or low water solubility. In 1992, our laboratory first reported a vanadyl complex with significant water solubility, bis(maltolato)oxovanadium(iV), abbreviated as BMOV or VO(ma)2.  43  Other potentially useful properties of this complex include neutral  charge and lipophilicity, a combination designed to enhance Gl absorption, probably through a passive diffusion process. BMOV has been shown to be effective in lowering plasma glucose at a lower dose than its parent compound, vanadyl sulfate, and to be non toxic over a  -10-  References on p. 35  Chapter 2  six-month period of administration in STZ-diabetic rats. '  44 45  Both oral gavage and  intraperitoneal (i.p.) administrations indicate that BMOV is two to three times more potent than vanadyl sulfate.  46  The pro-ligand maltol was used for its lack of toxicity. It is an  approved food additive in Canada, the U.K. and the U.S.A. The crystal structure of BMOV showed a square pyramidal geometry, and the solution chemistry studies of this complex have also been reported  47  The stability constants of VO(ma)2 (BMOV) in water were  determined and will be reported in this chapter.  CH  3  BKOV (VO(ka) )  BMOV (VO(ma) )  2  2  A similar vanadyl complex, bis(kojato)oxovanadium(IV) abbreviated as BKOV or VO(ka)2, was synthesized in our group, and its biological activity has also been explored. '  48 49  Kojic acid is a naturally occurring compound with a chemical structure similar to that of maltol, but the former is more hydrophilic than the latter due to the presence of an extra hydroxyl group. The stability constant determinations of this complex will also be reported in this chapter. Since BMOV displays favourable chemical and physiological properties, we were interested in its biodistribution following oral or i.p. administration in rats. We prepared BMOV and VS, each containing V as a tracer. V has a half-life of 16 days, and decays to 48  4  non-radioactive Ti by means of positron and gamma emission (y = 511, 983, 1312 keV). 48  -11 -  References on p. 35  Chapter 2  4  V was isolated as non-carrier added VS; the compounds used in these biodistribution 48  50  studies were carrier-added VS and V-BMOV. Incorporation of V into both BMOV and 48  48  48  VS permitted direct comparison of the uptake and tissue distribution characteristics of these two compounds. Previous studies have looked at biodistributions following intratracheal, intragastric or intravenous (i.v.) administration of radiolabeled V tracers over periods of 48  several days to several weeks. ' '  9 51 52  In our study, early time points were emphasized to  elucidate the curve of uptake, and comparison of the two compounds over a period of 24 h permitted prediction of kinetic parameters in a variety of tissues. In order to gain an integrated picture of whole body vanadium biolocalization, compartmental analysis of the tracer data was undertaken.  53  An existing compartmental  model of vanadium metabolism was used as a starting point for model construction, using 54  SAAM II software (SAAM Institute Inc., Seattle, WA).  55  The results of biodistribution  studies and kinetic analysis using compartmental modelling are reported in this chapter.  2.2. Experimental Materials. Chemicals and solvents used were reagent grade (Fisher, Aldrich) and were used without further purification unless otherwise noted. VOS04-3H20 was obtained from Aldrich, and maltol (3-hydroxy-2-methyl-4-pyrone, Hma) and kojic acid (5-hydroxy-2hydroxymethyl-4pyrone, Hka)fromSigma or Pfizer. Atomic absorption standard vanadyl solution was obtainedfromAldrich. With the exception of drinking water, all water was deionized (Barnstead D8902 and D8904 cartridges) and distilled (Corning MP-1 Megapure Still).  V, in the form of non-earner added VS, was prepared by Zeisler and Ruth at 50  TRIUMF (Vancouver, B.C., Canada).  -12-  References on p. 35  Chapter 2  Instrumentation.  UV/vis spectra were recorded on a Shimadzu UV-2100  spectrophotometer. The activity of V in the biodistribution studies was counted in a well y48  counter (Canberra Packard, Cobra II, Auto-gamma/3" crystal). Potentiometric equilibrium measurements.  The potentiometric determination  methods of the pK of maltol and of the second stepwise stability constant of VO(ma)2 (K ) a  2  are identical to those for kojic acid. Thus, only the procedure involving maltol will be described. Potentiometric measurements of maltol in the absence, and presence, of vanadyl ion were performed with a Fisher Acumet 950 pH equipped with an Orion Ross glass and calomel reference electrodes. The electrode was calibrated before each titration, and often afterwards, by titrating a known amount of aqueous HC1 with a known concentration of NaOH. A plot of mV (measured) vs pH (calculated) gave a working slope and intercept so that the pH could be read as -log [H ] directly. A Metrohm automatic burette (Dosimat 665) was used for the NaOH additions and the burette and pH meter were interfaced to a PC such that each titration was automated. The temperature of the solutions in covered, water jacketed beakers was kept constant at 25.0 ±0.1 °C by a Julabo circulating bath. The ionic strength was fixed at 0.15 M NaCl. Argon, which had been passed through 10% NaOH, was bubbled through the titration solutions to exclude CO2. Maltol was checked for purity by ' h NMR spectroscopy and elemental analysis (C, H) before titration. The vanadyl solution was prepared by dilution of its atomic absorption standard. Sodium hydroxide and sodium chloride were added to neutralize the excess acid present and to bring the ionic strength to 0.15 M Na . The vanadyl solution was then titrated with standardized NaOH from pH 2 to 2.5 to obtain the amount of excess acid present by Gran's method. NaOH solutions (0.1 M) were prepared from dilution of 50%) NaOH with 56  - 13 -  References on p. 35  Chapter 2  freshly boiled distilled, deionized water and standardized potentiometrically against potassium hydrogen phthalate. The ratio of ligand to metal used was 1:10 < L:M < 10:1. Concentrations were in the range 1 - 10 mM. A total of six titrations were performed for maltol alone, and ten titrations defined the V(IV) - maltol equilibria. Maltol was titrated over the range 3 < pH < 9, while the vanadyl-maltol solutions were titrated from pH 2 to 4. Vanadium(IV) hydrolysis occurs above pH 4 when ligand to metal ratios are less than 2, and this hydrolysis is slow and ill defined. Also, in the higher pH regime, the vanadyl maltolate complexes and the vanadyl hydrolysis products were susceptible to oxidation. Complexation was rapid (1-3 min per point to give a stable pH reading) between pH 2 and 4; however, above pH 4, equilibrium was slow owing to hydrolysis/oxidation (vide supra). The deprotonation constant for maltol and the vanadyl-maltol stability constants were determined by using the program BEST.  57  This program sets up simultaneous mass-balance  equations for all the components present at each addition of base and calculates the pH at each data point according to the current set of stability constants and total concentrations of each component. The best fit of the data consisted simply of the two metal-ligand species +  +  2  +  VO(ma) and VO(ma) . The hydrolysis species VO(OH) and [(VO) (OH) ] were included 2  2  2  in the calculation, but these did not form to any appreciable extent under the conditions 58  employed. A plot n(n = moles of bound ligand per mole of metal ion) vs log [ma] showed -  all the data coinciding to a single curve which plateaued at n = 2 indicative of a system in which only binary metal - ligand species prevail (see Figure 2.5 on p. 22). Typically, 100 data points were collected in the buffer region of metal-ligand complexation.  -14-  References on p. 35  Chapter 2  Spectrophotometry. Similarly, only the procedure for the first stepwise stability constant (Ki) for VO(ma) will be described since an identical procedure was used for +  VO(ka) . Since the 1:1 vanadyl maltolate complex was partially formed even at pH 2, +  variable pH spectrophotometry was employed to obtain an accurate value for the 1:1 stability constant.  This was necessary since any error in the total acid concentration would be  absorbed in this constant. Calculation of K, by variable pH spectrophotometry requires accurate knowledge of the total vanadium and maltol concentrations, as well as accurate pH measurement, but is independent of any excess acid present (from the vanadyl standard solution). From potentiometric measurements employing an excess of vanadyl ion, a range of K, values was obtained with low precision (± 0.2 log units); however, this value was used to obtain the conditions in which the only species present were vanadyl, maltol, and VO(ma) . Using these conditions (L:M < 0.2, pH 2 - 3), the effect of pH in the absorbance +  range 315 - 335 nm was studied. Neither vanadyl nor maltol absorb in this range, hence the +  change in absorbance was because of VO(ma) .  The equilibrium constant was written in  +  terms of VO(ma) (eq 1).  [VO(ma) ] [H ] +  £  +  _ 1  (1) Ka ( C  2 + v o  - [VO(ma) ]) ( C +  - [VO(ma) ]) +  Hma  Here, K refers to the K of maltol and C 2+ and C a  a  VQ  H m a  to the total vanadium and maltol  +  concentrations, respectively. Since [VO(ma) ] = Abs/s in the absorbance range studied, s and Kj could be varied iteratively as a function of pH until consistent results were reached.  -15-  References on p. 35  Chapter 2  This was done at five wavelengths utilizing 11 pH points at 3 different L:M ratios (see Figure 2.4 on p. 21). Methods for biodistribution studies of V-labelled compounds in rats. Three sets 48  of experiments were run: an initial oral gavage (experiment A), a second oral gavage experiment where excreta were collected (experiment B) and an intraperitoneal (i.p.) (experiment C). Animals and diets. Male Wistar rats (University of British Columbia Animal Care Unit, Vancouver, B.C., Canada) weighing between 190 and 220 g were housed in polycarbonate cages. During experiments A and C, rats were housed three per cage in polycarbonate cages.  For experiment B, animals were transferred to individual  polycarbonate metabolic cages immediately following administration of the compound. These cages were equipped with fecal and urinary collection containers. The animals were kept in a room maintained at 22-25 °C on a 12-h light-dark cycle and were cared for in accordance with the principles and guidelines of the Canadian Council on Animal Care. A commercial diet (Purina rat chow, Ralston, Purina, St. Louis, MO) and tap water were offered ad libitum for several days prior to, and throughout, the experimental period. Preparation of carrier-added V-labelled complexes. In the initial oral and i.p. 4  48  experiments (experiments A and C, respectively) carrier-added VS was prepared by mixing 48  an appropriate volume of VS (in 0.01 M H S0 ) with 0.2 mmol (50 mg) of VOS0 .3H 0. 2  4  4  2  Immediately before administration of the solution, the pH was adjusted to between 3.5 and 4 by dropwise addition of 1 M NaOH. The total volume was then made up to 12 mL with water. 48  Carrier-added  V-BMOV in the initial oral and i.p. experiments (A and C) was -16-  References on p. 35  Chapter 2  synthesized as follows: to the mixture of 0.2 mmol (50 mg) of VOS0 .3H20 and three to 4  48  four equivalents of maltol was added an appropriate volume of VS (in 0.01 M H S0 ). 2  4  With rapid stirring, 0.5 mL of 1 M NaOH was added dropwise to the suspension at 80 °C. This temperature was maintained for another 10 min, so that the reaction mixture was almost 48  dry.  V-BMOV was isolated as a gray-green solid. Immediately before administration, it  was dissolved in 16 mL of water. 48  In the preparation of  V-BMOV in the subsequent oral gavage administration  (experiment B), 0.08 mmol (18 mg) of VOS0 .3H 0 and four equivalents of maltol were 4  2  mixed in water. After dissolution of the solid, 0.8 mL of 0.2 M NaOH was added dropwise 48  over a 10 min penod. To this mixture was added an appropriate amount of VS (in 0.005 M H S0 ). The pH of the solution was finally adjusted to between 3.5 and 4 with 0.2 M NaOH 2  4  48  before gavage.  VS in experiment B was prepared by dissolving 0.07 mmol (15 mg) of 48  VOS0 .3H 0 and 4  2  VS (in 0.005 M H S0 ) in water. The pH of this solution was adjusted 2  4  to 4 by adding 0.2 M NaOH. 48  48  Biodistribution studies. For experiment A, V-BMOV (3.8 mg) or VS (2.6 mg) 0.012 mmol V/animal, containing 200 pCi per animal for each compound, were 48  48  administered by oral gavage. For experiment C, V-BMOV (1.9 mg) or VS (2.2 mg) 48  0.006 mmol V and 0.010 mmol V/animal respectively, containing 100 pCi  V for  48  BMOV/rat or 150 pCi V for VS/rat were administered by i.p. injection. In these two experiments (A and C), rats (n=3/time point) were sacrificed and tissue and blood samples were collected at 15, 30 min and 1, 4, and 24 h time points following administration. In 48  48  experiment B, V-BMOV (3.2 mg, 0.010 mmol), or VS (2.0 mg, 0.009 mmol), containing - 17 -  References on p. 35  Chapter 2  48  170 pCi of  48  V/rat or 50 pCi of  V/rat, respectively, were administered, also by oral  gavage. Collection times in experiment B were 2, 6, 10, 14, 19, and 24 h following administration. At each time point in all studies, three rats were anaesthetized with halothane, blood was obtained from the carotid artery, and the anaesthetized animals were then killed by cervical dislocation. Tissues were collected and placed in pre-weighed receptacles. Liver, kidney, muscle, spleen, lung, testicle, bone, heart and brain samples were rinsed in normal saline, weighed and blotted dry before freezing.  In the second oral gavage study  (experiment B), urine, fecal, stomach and Gl contents were also collected. All tissue 48  samples were stored frozen at -20 °C until counted for  V activity. The activity was  recorded in a well y-counter. Percentage of administered dose (%AD) was calculated as a fraction of the 'standard counts' for that time period, determined by counting the equivalent volume of radiolabeled solution with the same set of samples (Figure 2.8 on p. 25, as %AD/organ, Figure 2.10 as %AD/g wet weight of tissue on p. 28). The total carcass radioactivity was not analyzed. In this carrier-added study, calculating %AD corrects for 48  variation of two to three times in the amount of V and even in a small variation in the dose of cold vanadium. The total blood (7.8% of body weight), bone (12% of body weight) and muscle (45%» of body weight) masses were calculated according to reported methods.  59  48  Kinetic modeling. Simulation of V uptake, distribution and excretion was carried out using SAAM II™ (Simulation, Analysis and Modeling) software (SAAM Institute, Seattle, WA), V I.O.2. '  53 55  Data, in %AD/g tissue, from the initial oral gavage study  (experiment A) were used to modify a model of vanadium metabolism previously published. The fractional transfer coefficients (ky) derived from experiment A were then 54  -18-  References on p. 35  Chapter 2  used as a starting point for modeling the data from the second oral gavage study (experiment B). Initial values were varied by iteration until a consistent set of parameters was obtained for each compound, taking into account the greater variability of the second data set for each compound tested. Experiment C, with the overall highest coefficient of variation (CV=0.9), was modelled last as an extension of the combined oral gavage studies, according to a previously established paradigm. In accordance with standard modeling nomenclature, 60  61  ley represents the fraction of material moving from compartment j to compartment / per unit time (hour ). Residence time is equivalent to the inverse of the ley for those compartments 1  having only one egress; for blood, residence time is defined as H'Llen where compartment 1 represents blood (Figure 2.9. on p. 26, vide infra).  62  Absorption of vanadium 24 h post  administration was calculated as (intake - fecal excretion) as a percentage of administered oral dose.  62  2.3. Results and Discussion 2.3.1. Stability constant determinations of vanadium(IV) complexes  The solution equilibria in the vanadyl-maltolate and vanadyl-kojate systems were studied in the pH range 2-4 to avoid any problems with hydrolysis or oxidation. This pH range was adequate for determining the 1:1 and 2:1 (L:M) formation constants since maltol and kojic acid are both strong chelators. The equations used to define the deprotonation constants (pK ), the stepwise stability constants (Ki and K ), and the overall stability a  2  constants (0 ) for both systems are: 2  -19-  References on p. 35  Chapter 2  Ka  HL V0  VO(L) V0  Table 2.1.  2+  +  2+  U  -  H  .  VO(L)  +  L"  . "  +  21/  .  +  z  -  +  (2) (3) (4)  2  (5)  a  2  8.46(2)  7.68(3)  logKi  8.80(2)  7.61(10)  logK  7.51(2)  6.89(6)  16.31(3)  14.50(16)  2  L"  Deprotonation Constants (pK 's) and Stability Constants of VOL .  pK^  g  VO(L)  2  L = ka  lo p  +  VO(L)  L = ma  2  +  The number in parentheses refers to 3a in the last digit.  Both maltol and kojic acid have only one ionizable proton each; the latter has a lower pK  a  than the former due to the presence of electron-withdrawing hydroxymethyl (-CH OH) 2  group in kojic acid. The first stepwise stability constants (K[) for both systems were determined spectrophotometrically, and the second stepwise stability constants (K ) were obtained by 2  potentiometric titrations. The variable pH (2-3) UV-spectra of VO(ma) (k= 250-360 nm) +  in the determination of K i are presented in Figure 2.4. The inset shows the results of experimental (points) absorbances vs pH, and solid lines are fits (by varying Ki and s o(ma) ) +  V  to the experimental data. - 20 -  References on p. 35  Chapter 2  2.0-,  1.5  H.  1.0  H  0.5  H  pH=3.01  3  pH=1.99  o.o  I  T  260  300 320 Wavelength (ran)  280  340  360  Figure 2.4. Variable pH (2-3) UV-spectra of VO(ma) (k= 250-360 nm) and experimental +  absorbances (pointsVcalculated (lines) absorbances vs pH (inset). The L:M ratio is 0.11.  The overall titration curves as a plot of n vs the log of free ligand concentration for L:M ratios ranging from 0.17 to 10 (for both ligands) are shown in Figure 2.5. The coincidence of all the data to one curve in each of the two systems is indicative of the high quality of the data collected, and of the simplicity of the system in that there are only binary metal-ligand species present (namely ML and ML ) and no protonated or hydroxo complexes in the pH 2  range studied.  63  Although K) > K , at a 2:1 (L:M) ratio, the VO(L) (1:1 L:M) species +  2  dominates only at low pH, and the dominant species at physiological pH under reducing conditions should be VO(L) , as shown by the respective speciation diagrams (Figure 2.6 2  and 2.7) extrapolated to pH 8.  -21 -  References on p. 35  Chapter 2  -10  -9  -8 log [I/]  -7  -6  -5  -4  Figure 2.5. Titration curves as a plot of n vs the log of free ligand concentration for L:M ratios ranging from 0.17 to 10 for both the V0 /Hma and V0 /Hka systems. 2+  -22-  2+  References on p. 35  Chapter 2  2  3  4  5  6  7  8  PH Figure 2.7. Speciation diagram for the V0 /Hka system (1 mM V 0 , 2 mM Hka). 2+  2+  The solution studies of V0(ma)2 and V0(ka)2 are very similar, as are the glucoselowering abilities of these two compounds. In the acute oral gavage studies in STZdiabetic rats, VO(ma)2-treated animals were able to maintain euglycemic plasma glucose levels better than VO(ka)2-treated animals 24 h after administration. This was also true in 49  the chronic studies where VO(ma)2 more significantly reduced plasma glucose levels from week 2 though week 6 than did VO(ka)  4 9  2  -23 -  References on p. 35  Chapter 2  2.3.2. Biodistribution studies of V-labelled vanadyl sulfate (VS) and BMOV 48  48  Overall, for oral administration the highest concentrations of V (expressed as % administered dose/g wet weight of tissue (herein after abbreviated as %AD/g)) were seen in kidney, followed by bone, blood, liver, spleen and heart (all data available in Table A1-A6 (Appendix) and for data as %AD/organ see Figure 2.8). The concentrations in these tissues 48  did not exceed 0.6 %AD/g at any one time point (vide infra). In most other tissues, V concentration did not exceed 0.1 %AD/g of oral dose. The concentration of V in bone 48  exceeded that of kidney at 24 h after oral gavage. Coefficients of variation (CV) for experiment B were considerably higher than those for experiment A (average CV for 48  experiment A=0.3; for experiment B=0.5).  I.p. injection of  V-labelled compounds  (experiment C) resulted in a higher apparent uptake in kidney and bone (not exceeding 1.6 %AD/g tissue) with little change in uptake for most other tissues between 4 and 24 h after injection, compared to either of the oral gavage experiments (refer to Table A1-A6 in the 48  Appendix).  The relative concentrations of  V in bone and kidney following i.p.  administration were also considerably higher than those following an oral dose (vide infra). 48  Soft tissue uptake from oral gavage of VS and  48  V-BMOV, as %AD/organ (Figure  2.8) based on average total tissue or organ weights, was greatest overall in liver > kidney > 48  spleen > heart > testes > lung. The highest V content at 24 h following oral gavage was seen in bone, liver and kidney (Figure 2.8); however, muscle also took up appreciable amounts of V (Figure 2.8), due to the high percentage of body weight (45%) represented 4  by muscle.  -24-  References on p. 35  Chapter 2  ssop pajsjsiuiuipE %  ssop parajsraiuipu %  c  -25-  References on p. 35  Chapter 2  Figure 2.9. Compartmental model of vanadium metabolism (modified from Patterson et  A 13-compartment model (including urinary and fecal 'sinks') adequately described 48  48  the data for both V-BMOV and VS carrier-added doses by oral gavage (Figure 2.9). High variation in the data, both within data sets, and between experiments A and B, precluded a more complex model.  61  Hence, the tissues represented (see Figure 2.9) were  chosen based on previous studies showing uptake into these tissues.  64  Remaining tissues  sampled (heart, brain, spleen, lung, pancreas and muscle) were included in a 'lumped' * Enclosed spaces represent compartments that are kinetically homogeneous and distinct from other compartments. Numbers within these spaces correspond to compartment numbers in the mathematical model. Arrows represent transfer pathways. Compartment 7 represents a combination of soft organ tissues: heart, lung, brain, pancreas, and muscle. Sampling sites included in construction of the model were: liver, kidney, bone, and testes. Blood, urine and fecal data were used to verify the model. -26-  References on p. 35  Chapter 2  compartment, labelled as compartment 7. A kinetic heterogeneity in kidney was apparent, with the data fitting best to a 2-compartment kidney. The 3-compartment Gl represents a delay between oral input and fecal output and does not signify physiological differences between these compartments.  65  Compartmental analysis revealed a pattern of increased uptake from an oral dose of 48  V-BMOV compared to that of VS. The greatest difference in uptake was seen in liver, 48  which had a four times greater uptake of V-BMOV relative to VS. The schematic of the 48  48  model (Figure 2.9) shows oral input proceeding through a 3-compartment Gl, with absorbed 48  V taken up into the blood and from there distributed to short- and long-stay tissues.  Unabsorbed V was excreted via the feces, while excretion of absorbed V was via the 48  48  urine through the second kidney compartment. Recirculation of V is possible both through 48  biliary secretion from the liver, and resecretion back to blood from the second kidney compartment. Simulations of tracer disappearance using the combined data sets, in %AD/g tissue, are presented in Figure 2.10 ("V-BMOV (A) and VS (B)). Most tissues showed a 48  gradual uptake peaking at 2 - 6 h after gavage, with a decline thereafter; however, bone, liver and kidney remained high at 24 h, indicating continued accumulation or slow clearance.  -27-  References on p. 35  Chapter  2  srissii 3/9SOp pajajsmiiupB % -28-  References  on p.  35  Chapter 2  Apparent absorption of V-BMOV was greater than that of VS. The primary route 4  48  of elimination was in the feces. Based on compartmental analysis of combined data sets (experiments A and B), 75% of VS and 62% of V-BMOV were excreted unabsorbed in the feces within 24 h following oral gavage. Although the time frame of this experiment was too short to determine accurately absorption, the model-predicted apparent vanadium absorption was 25% for VS and 38% for V-BMOV. These values are most likely a considerable overestimate of vanadium absorption since they are based on estimates from 24 h data sets only. The model-predicted absorption values were adequate to indicate a trend towards greater absorption of V-BMOV compared to VS, approximately 1.5 times 48  48  greater.  Table 2.2. Relative Concentrations of V 24 h after Oral Gavage (% AD/g tissue). 48  Liver  Kidney  Bone  VS  0.021  0.086  0.11  48  V-BMOV  0.082  0.12  0.33  48  V-BMOV/ VS  3.9  1.4  2.9  48  48  Percent administered dose (%AD) per gram tissue as predicted by model (Figure 2.9) at 24 h time point. The average of V-BMOV7 VS for liver, kidney and bone was 2.7. 48  48  The ratios of "V concentrations (in %AD/g) in bone:kidney:liver 24 h following oral gavage predicted by the model were 0.33 : 0.12 : 0.082 for V-BMOV and 0.11 : 0.086 : 48  0.021 for VS (Table 2.2). Thus, the proportions of V taken up by bone, kidney and liver 48  4  following "V-BMOV treatment were approximately three, 1.4 and four times, respectively,  -29-  References on p. 35  Chapter 2  greater than that following VS treatment. Averaging the increased uptake into liver, 48  kidney and bone, the ratio of uptake of V-BMOV to VS was 2.7. Taking into account 4  48  total tissue weight, the principal uptakes of V from an oral dose of BMOV vs. VS were 4  liver (0.82% vs. 0.21%), kidney (0.23% vs. 0.17%), muscle (1.14% vs. 0.67%), blood (3.55%) vs. 2.73%) and bone (8.62% vs. 2.99%), based on model-predicted compartmental masses at 24 h following gavage. Residence times of V (and the fractional transfer coefficients on which they were 4  based) for the tissues modeled are given in Table 2.3. The shortest residence times were in blood, and the longest in bone. Residence times in blood were calculated to be 7 min for 4  V-BMOV and 5 min for VS; in bone, residence times of 31 days for V-BMOV and 11 48  48  days for VS were calculated. 48  These results clearly demonstrate the increased tissue uptake from an oral dose of V-BMOV compared with that of VS. This is in accord with comparisons in tissue uptake between iron sulphate and the iron maltol complex, tris(maltolato)iron(III).  66-68  These studies have shown that by forming a stable, neutral complex with Fe , maltol 3+  enhanced iron absorption across the rat small intestine in vivo, and that not only was the iron held in soluble form, but it was also efficiently carried into the mucosa. At the same time, regulatory processes to prevent iron overload were not bypassed. In our study, complexation of labelled vanadium(IV) with maltol resulted in enhanced uptake and slower excretion of "V-BMOV as compared to "Vs (Figure 2.10, and Tables 2.2 and 2.3). Absorption was also greater with "V-BMOV than with "Vs. This greater absorption and tissue uptake are also consistent with the increased pharmacological potency in lowering in vivo blood glucose levels seen previously.  46  -30-  References on p. 35  Chapter 2  Table 2.3. Fractional Transfer Coefficients between Compartments of V Model (h"), and 48  1  4ft  Residence Times (11) of V in Key Compartments. VS  V-BMOV  Transfer Coefficients  48  ki3,2 kidneyi->kidney2  0.75 ± 0.28  0.26 ± 0.05  ki 4  0.26 ± 0.09  0.15 ±0.04  ki,5 testes—>plasma  0.63 ±0.13  0.29 ±0.10  k i ,6  0.0038 ± 0.0022  0.0028 ±0.0011  kij3 kidney2->plasma  4.9 ±2.3  0.63 ± 0.50  k i3  7.4 ± 0.7  5.5 ±0.50  Residence Times  48y  48  Hi blood*  5.0 min  7.0 min  11  2  kidney i  4.9 min  9.7 min  11  4  liver  3.8 h  6.8 h  11  5  testes  1.7 h  3.4 h  11  6  bone  11 d  31 d  1.3 h  3.8 h  ;  3;  liver->plasma  bone->plasma  kidney2^urine  1113 kidney ** 2  48  S  V-BMOV  kj represents the fraction of a vanadium pool movingfromcompartment j to compartment / per unit time (h") 1  ± SE for variation between simulation runs. Residence time (11) is calculated as the inverse of kg from that compartment. Kidneyi and kidney  2  represent kinetically distinct compartments which could be either  physiologically or biochemically distinguishable. No anatomical separation is implied. Numbers correspond to compartment numbers in the model (Figure 2.9). * 111 = 1/Ikj,i; ** 11 = l / £ k 2  -31 -  iil3  .  References on p. 35  Chapter 2  The long residence time of V in bone (11.1 d from "Vs and 31.3 d from "V4  BMOV) predicted by our model is in agreement with earlier studies. '  Subcutaneous  54 69  injection of rats with V-vanadate (1.8 mgV/kg) analyzed with a 2-compartment model for 4  each tissue predicted a half-life for bone of 376 h (15.6 d), which would be equivalent to 69  a residence time of 22.6 d (ti/2 = ln2 x II). Prediction of a previous vanadium model  54  (assuming that the unspecified long-stay tissue in the model of Patterson et al represents bone) was >lfj4 hours, or approximately 42 d, also reasonably close to the residence times predicted by our model. Variability within data sets, and between the first and second oral gavage studies (experiments A and B) resulted in high error terms for the fractional transfer coefficients representing movement of vanadium between compartments, and as a consequence, also for calculated residence times. In another study, at 24 h post injection, the percent of administered dose (of V48  vanadyl chloride added to ammonium metavanadate) in blood was 1.25%, in bone was 17.9% and in muscle was 2.65%, as compared to 3.55% in blood, 8.62% in bone, and 69  1.14% in muscle for V-BMOV in our study. In the report of Conklin et al, oral gavage of 48  V - V 0 (40 pg/rat, -0.3 mg/kg) resulted in 0.65% AD in bone 3 d after dosing. The 70  2  5  low solubility of V2O5 compared to vanadate, vanadyl, or BMOV is probably the cause of this low localization; however, the longer time frame is also a factor.  Hamel and  Duckworth predicted longer residence times than we calculated for a variety of soft 71  tissues (bone vanadium was not measured) in the rat based on patterns of uptake and redistribution of low levels of dietary vanadium, as detected by neutron activation analysis over a longer time period. The significant difference in dose and the chronic, rather than acute, nature of the study, may explain this discrepancy. These researchers also observed 71  -32-  References on p. 35  Chapter 2  that 2.7% of a gavage dose was in the blood (total) at 24 h, which is in a good agreement with our calculations. The kinetic heterogeneity in kidney predicted by our model suggests that the longer stay kidney compartment may represent stored vanadium, while the short stay kidney compartment may represent a vanadium excretion pathway. All studies to date indicate that kidney is a primary target of vanadium localization, along with liver and bone. ' '  9 51 72  The amounts of V predicted to be excreted in the feces 24 h following an oral dose 4  (75% for VS and 62% for V-BMOV) are in line with the amount measured by Bogden et al.,  11  in which 59% of an ingested dose of sodium metavanadate was recovered in the  feces. Oral gavage of rats with 5pmol V-Na3V04 resulted in a 4-d recovery of V, 69% 4  48  in stool and 12.5% in urine. The short time-frame of our experiment (24 h) made a more 52  accurate determination of absorption impossible. Based on other studies, actual absorption of orally administered vanadium is likely to be much lower (1-10%).  73  The pattern of  unexcreted V in tissues was kidney > bone > liver > intestine > muscle (in %AD/g tissue), 48  and was unchanged when administration was i.p. rather than by gavage. This is in agreement with earlier studies, '  52 74  showing a similar pattern of tissue distribution  following V administration, whether oral, i.p., or i.v. The increase in label retention up to 4  approximately 4 h seen in our studies was also apparent in a previous V study in rats, 4  51  although since the latter study was via i.v. injection, much more V was excreted in the 48  urine than in the feces. The highest concentration of V-vanadate in blood was seen at 2 h 48  post-gavage in another study.  69  ' In conclusion, these results showed the distribution of vanadium in different body tissues following oral or i.p. administration, with concentration in bone > kidney > liver >  -33 -  References on p. 35  Chapter 2  spleen > heart > testes > lung > pancreas > brain at 24 h. Compartmental modeling permitted detection of significant patterns in a particularly 'noisy' data set and also allowed prediction of approximate residence times for key tissues. Tissue distribution patterns from 4  V-BMOV differed from VS, with relatively higher V ratio in liver to kidney from the 48  48  vanadium coordination complex. Results of this analysis emphasize the importance of early blood collection times to define the curve of vanadium disappearance from blood and, by contrast, a longer time frame to chart vanadium accumulation in bone more accurately. Tissue uptake after oral gavage of V-BMOV was approximately two to three times higher 48  than with VS (Table 2.2). This result is consistent with the increased acute glucose48  lowering potency of two to three times seen with BMOV compared with VS.  -34-  46  References on p. 35  Chapter 2  2.4. References  1)  Bertrand, R. Bull. Amer. Mus. Nat. Hist. 1950, 94, 403.  2)  Cole, P. C ; Eckert, J. M.; Williams, K. L. Anal. Chim. Acta 1983,153, 61.  3)  Collier, R. W. Nature 1984, 309, 441.  4)  Henze, M. Z. Physiol. Chem. 1911, 72, 494.  5)  Wever, R.; Krenn, B. E. In Vanadium in Biological Systems; Chasteen, N. D., Ed.; Kluwer Academic Publishers: Dordrecht, The Netherlands, 1990, p. 81.  6)  Smith, B. E.; Eady, R. R; Lowe, D. J.; Gormal, C. Biochem. J. 1988,250, 299.  7)  Nechay, B. R. Ann. Rev. Pharmacol. Toxicol. 1984, 24, 501.  8)  Ramasarma, T.; Crane, F. L. Curr. Top. Cell. Reg. 1981, 20, 247.  9)  Sabbioni, E.; Marafante, E. Bioinorg. Chem. 1978, 9, 389.  10) Butler, A. R; Carrano, C. J. Coord. Chem. Rev. 1991,109, 61. 11) Boyd, D. W.; Kustin, K. Adv. Inorg. Biochem 1984, 6, 311. 12)  Simons, T. J. B. Nature 1979, 281, 337.  13) Mimoun, H.; Saussine, L.; Daire, E.; Postel, M.; Fischer, J.; Weiss, R. J. Am. Chem. Soc. 1983,705,3101. 14) Djordjevic, C ; Puryear, P. C ; Vuletic, N.; Allelt, C. J.; Sheffield, S. J. Inorg. Chem. 1988, 27, 2926. 15) Djordjevic, C ; Lee, M.; Sinn, E. Inorg, Chem. 1989, 28, 719. 16) Sternberg, R. Acta Chem. Scand. 1986, A40, 168. 17)  Macara, I. G. Trends Biochem. Sci. 1980, 5, 92.  18) Cantley, L. C , Jr.; Josephson, L.; Warner, R.; Yanagisawa, M.; Lechene, C ; Guidotti, G. J. Biol. Chem. 1977, 252, 7421.  -35-  Chapter 2  Chasteen, N. D. Struct. Bond. (Berlin) 1983, 53, 105.  Boas, L. V.; Pessoa, J. C. In Comprehensive Coordination Chemistry; Wilkinson, G., Ed.; Pergamon Press: New York, 1987; Vol. 3, p. 453-583. Stiefel, E. I.; Dori, A.; Gray, H. B. J. Am. Chem. Soc. 1967, 89, 3353. Lyonett, M. Presse Medicate 1899, / , 191.  Posner, B. I.; Shaver, A.; Fantus, I. G. In Antidiabetic Agents; Bailey, C. J., Flatt, P. R., Eds.; Smith Gordon, 1990, p. 107. Shechter, Y.; Meyerovitch, J.; Farfel, Z.; Sack, J.; Bruck, R; Bar-Meir, S.; Amir, S.; Degani, H.; Karlish, S. J. D. In Vanadium in Biological Systems; Chasteen, N. D., Ed.; Kluwer: Dordrecht, 1990, p. 129. Shechter, Y. Diabetes 1990, 39,1. Orvig, C ; Thompson, K. H.; Battell, M.; McNeill, J. H. Metal Ions Biol. Syst. 1995, 31, 575. Tolman, E. L.; Barris, E.; Bums, M.; Pansisni, A.; Partridge, R. Life Sci. 1979, 25, 1159. Shechter, Y.; Karlish, S. J. D. Nature (London) 1980, 284, 556. Dubyak, G. R; Kleinzeller, A. J. Biol. Chem. 1980, 255, 5306. Clark, A. S.; Fagan, J. M.; Mitch, W. E. Biochem. J. 1985, 232,273. Duckworth, W. C ; Solomon, S. S.; Liepnieks, J.; Hamel, F. G.; Hand, S.; Peavy, D. E. Endocrinology 1988,122, 2285. Shechter, Y.; Ron, A. J. Biol. Chem. 1986, 261, 14945. Heyliger, C. E.; Tahiliani, A. G.; McNeill, J. H. Science 1985, 227, 1474.  -36-  Chapter 2  34) Domingo, J. L.; Gomez, M.; Llobet, J. M.; Corbella, J.; Keen, C. L. Toxicology 1991, 66, 279.  35) Kadota, S.; Fantus, I. G ; Deragon, G.; Guyda, H. J.; Posner, B. I. J. Biol. Chem. 1987, 262, 8252. 36) Kadota, S.; Fantus, G.; Deragon, G.; Guyda, H. J.; Hersh, B.; Posner, B. I. Biochem. Biophys. Res. Commun. 1987,147, 259.  37) Fantus, I. G.; Kadota, S.; Deragon, G; Foster, B.; Posner, B. I. Biochemistry 1989, 28, 8864. 38) Shaver, A.; Ng, J. B.; Hall, D. A.; Soo Lum, B.; Posner, B. I. Inorg. Chem. 1993, 32, 3109. 39) Posner, B. I.; Faure, R.; Burgess, J. W.; Bevan, A. P.; Lachance, D.; Zhang-Sun, G.; Fantus, I. G.; Ng, J. B.; Hall, D. A.; Soo Lum, B.; Shaver, A. J. Biol. Chem. 1994, 269, 4596. 40) Sakurai, H.; Tsuchiya, K.; Nukatsuka, M.; Kawada, J.; Ishikawa, S.; Yoshida, H.; Komatsu, M. J. Clin. Biochem. Nutr. 1990,8, 193. 41) Cam, M. C ; Cros, G. H.; Serrano, J.-J.; Lazaro, R.; McNeill, J. H. Diab. Res. Clin. Prac. 1993, 20, 111.  42) Watanabe, H.; Nakai, M.; Komazawa, K.; Sakurai, H. J. Med. Chem. 1994, 37, 876. 43) McNeill, J. H.; Yuen, V. G.; Hoveyda, H. R; Orvig, C. J. Med. Chem. 1992, 35, 1489. 44) Yuen, V. G.; Orvig, C ; Thompson, K. H.; McNeill, J. H. Can. J. Physiol. Pharmacol. 1993, 71, 270.  45) Dai, S.; Yuen, V. G.; Orvig, C ; McNeill, J. H. Pharmacol. Commun. 1993, 3, 311. 46) Yuen, V. G.; Orvig, C ; McNeill, J. H. Can. J. Physiol. Pharmacol. 1995, 73, 55.  -37-  Chapter 2  Al) Caravan, P.; Gelmini, L.; Glover, N.; Herring, F. G.; Li, H.; McNeill, J. H.; Rettig, S. J.; Setyawati, I. A.; Shuter, E.; Sun, Y.; Tracey, A. S.; Yuen, V. G.; Orvig, C. J. Am. Chem. Soc. 1995,117, 12759-.  48)  Zhou, Y.; M.Sc. Thesis; The University of British Columbia, 1993.  49)  Yuen, V. G.; Caravan, P.; Gelmini, L.; Glover, N.; McNeill, J. H.; Setyawati, I. A.; Zhou, Y.; Orvig, C. J. Inorg. Biochem. 1997, 68, 109.  50) Zeisler, S. K.; Ruth, T. J. J. Radioanal. Nucl. Chem., Letters 1995, 200, 283. 51)  Hopkins, L. L., Jr.; Tilton, B.E. Am. J. Physiol. 1966, 211, 169.  52)  Wiegmann, T. B.; Day, H.D.; Patak, R.V. J. Toxicol. Environ. Health 1982,10, 233.  53)  Berman, M.; Weiss, M.F.; Shahn, E. Biophys. J. 1962, 2, 289.  54)  Patterson, B. W.; Hansard, S.L., II; Ammerman, C. B.; Henry, P.R.; Zech, L.A.; Fisher, W.R. Am. J. Physiol. 1986, 251, R325-R332.  55)  Berman, M.; Weiss, M.F. SAAM Manual. Washington, D.C. Department of Health, Education and Welfare (NTH), 1978.  56)  Gran, C. Acta Chem. Scand. 1950, 4, 559.  57) Motekaitis, R. J.; Martell, A. E. Can. J. Chem. 1982, 60, 2403. 58) Baes, C. F.; Mesmer, R. E. The Hydrolysis of Cations; John Wiley & Sons: New York, 1976. 59)  Maddalena, D. J. TISCON, A Basic Computer Program for The Calculation of The Bioidistribution of Radionuclide-labelled Drugs in Rats and Mice; Australian Atomic  Energy Commission: Lucas Heights, Australia, 1983. 60) Thompson, K. H.; Scott, K.C.; Turnlund, J.R. J. Appl. Physiol. 1996, 81, 1404. 61) DiStefano, J. J.; Landaw, E.M. Am. J. Physio. 1984,246, R651.  -38-  Chapter 2  62)  Jacquez, J. A. Compartmental Analysis in Biology and Medicine; 2nd. Ed.; The University of Michigan Press: Ann Arbor, 1985.  63)  Rossotti, H. The Study of Ionic Equilibria; Longman: London, 1978.  64)  Dai, S.; Thompson, K. H.; McNeill, J. H. Pharmacol. Toxicol. 1994, 74, 101.  65)  Thompson, K. H.; Turnlund, J.R. J. Nutr. 1996,126, 963.  66)  Barrand, M. A.; Callingham, B.A. B. J. Pharmacol. 1991,102, 408.  67)  Barrand, M. A;, Callingham, B.A.; Dobbin, P.; Hider, R.C. B. J. Pharmacol. 1991,102, 723.  68)  Levey, J. A.; Barrand, M.A.; Callingham, B.A.; Hider, RC. Biochem. Pharmacol. 1988,57,2051.  69)  Al-Bayati, M.; Raabe, O. G.; Giri, S. N.; Knaak, J. B. J. Amer. Coll. Toxicol. 1991,10, 233.  70)  Conklin, A. W.; Skinner, C.S.; Felten, T.L.; Sanders, C.L. Toxicol. Lett. 1982,11, 199.  71)  Hamel, F. G.; Duckworth, W.C. Mol. Cell. Biochem. 1995,153, 95.  72)  Bogden, J. D.; Higashino, H.; Lavenhar, M..A.; Bauman, J.W., Jr.; Kemp, F.W.; Aviv, A. J. Nutr. 1982,112, 2279.  73) Nielsen, F. H. Metal Ions Biol. Syst. 1995, 31, 543. 74)  Sabbioni, E.; Marafante, E.; Amantini, L.; Ubertalli, L.; Birattari, C. Bioinorg. Chem. 1978, S, 503.  -39-  CHAPTER 3  Lanthanide(III) C o m p l e x e s w i t h H e x a d e n t a t e A m i n o p y r i d y l p h e n o l a t e Ligands  3.1. Introduction The lanthanides (Ln) consist of 14 elements in the periodic table from cerium to lutetium (Ce-Lu, Z = 58-71); for the purpose of this thesis chapter, lanthanum will be included although it is, strictly speaking, not a lanthanide. Along with yttrium, scandium and lanthanum, the lanthanides are also known by their misleading traditional name, the rare earths. Although the original minerals gadolinite and cerite are rare, the elements are not. The most abundant element in the lanthanide series is cerium (Z = 58) at about 66 ppm in the earth's crust, five times more abundant than lead. The radii of the  lanthanide(III)  1  ions undergo the "lanthanide contraction"  phenomenon: as the atomic number increases, the ionic radius decreases (see Table 3.1) due to imperfect shielding of the 4f-electrons. The radii of Ln(III) ions are similar to that of calcium (1.00 A), one of many biologically important cations. A l l have similar donor atom preferences and strong ionic bonding nature. Since Ca(II) ion has a lower charge density than the Ln(III) ions, complexes of the former possess weaker bonds. These similarities can be utilized to probe the role of C a  2+  in the biological systems by substituting it with the  lanthanides which have more diverse physical properties (vide infra). 2  -40-  References on p. 83  Chapter 3  Table 3.1. Effective Ionic Radii of Ln(III) Ions (A). Lanthanide(III)  3  Coordination number 7 8 1.10 1.160  La  6 1.032  9 1.216  Ce  1.01  1.07  1.143  1.196  Pr  0.99  —  1.126  1.179  Nd  0.983  —  1.109  1.163  Pm  0.97  —  1.093  1.144  Sm  0.958  1.02  1.079  1.132  Eu  0.947.  1.01  1.066  1.120  Gd  0.938  1.00  1.053  1.107  Tb  0.923  0.98  1.040  1.095  Dy  0.912  0.97  1.027  1.083  Ho  0.901  —  1.015  1.072  Er  0.890  0.945  1.004  1.062  Tm  0.880  —  0.994  1.052  Yb  0.868  0.925  0.985  1.042  Lu  0.861  —  0.977  1.032  Unlike transition metal complexes, those of the lanthanides are not restricted either in their coordination number or their geometries. The coordination number of Ln(III) in the solid state varies from three to twelve, although coodination numbers above six are 4  common.  The bonding in Ln(III) complexes is highly ionic; therefore, the resulting 5  coordination geometries and coordination numbers depend on the ligand (donor atoms, size, conformation, ligand denticity) and solvent. Much of the research in the chemistry of Ln(III) metal ions within recent years has focussed on their potential uses in bioinorganic chemistry and material  -41 -  science. ' '  1 6 7  References on p. 83  Chapter 3  Magnetic properties of the lanthanides have been extensively reviewed by Kahn.  8-10  A  concomitant growing interest has also been directed towards the design of polydentate chelating ligands capable of forming stable Ln(III) complexes for radiotheraphy in nuclear medicine because of the rich array of isotopes available,  11-15  such as ^Y*, Sm and 153  169  Yb.  This interest is also due to the application of Ln(III) complexes as contrast agents for magnetic resonance imaging (MRI), such as the Gd(III) complex with DTP A (DTP A = 16  N,N,N',N",N"-diethylenetriaminepentaacetic acid), whose commercial name is Magnevist™. Recent reviews of both applications are available in the November 1999 issue of Chemical Reviews.  17  We have been exploring the chemistry of Ln(III) ions with multidentate ligands, particularly Schiff bases, amine phenolates, amine phosphinates and amine pyridyl carboxylates.  18-20  In the process, a plethora of different coordination geometries around  Ln(III) centers has been discovered, including two (encapsulated dimer and sandwich dimer) which contain dinuclear Ln(III) complexes with bridging phenolate oxygen atoms and geometries which can be controlled by appropriate ligand architecture (Scheme 3.1).  HOOC—y y N HOOC  y y  1  y—COOH  y  N  N  y  ^—COOH  HOOC DTPA  * Y is not in the Ln series; it is located above La in the periodic table. Y(III) is often mentioned together with Ln(III) due to their similarities in physical and chemical properties. It is actually a rare earth.  -42-  References on p. 83  Chapter 3  Capped Sandwich dimer  Scheme 3.1.  Compartmental Schiff bases, - including some acyclic examples, ' 21  22  22 23  have also  been used to simultaneously incorporate two or more Ln(III) and a combination of Ln(III)3d-metal ions; the resulting species also usually contain bridging phenolate oxygen atoms. The phenolate and alkoxo moieties of  2,6-bis[(dimethylamino)methyl]-4-methylphenol  (bdmmp) and l,3-bis(dimethylamino)-2-propanol (bdmapH), respectively, and hydroxo are also found as bridging ligands in Ln(III)-3d-metal ions aggregates. ' Ln(III) complexation 24 25  with hexahomotrioxacalix[3]arene macrocylic ligands have been known to form dimers containing bridging aryloxide oxygen atoms as well.  26  Other examples of polynuclear  Ln(III) complexes are those with bridging acetates, ' and with bridging trifluoroacetates 27 28  -43 -  References on p. 83  2 5  Chapter 3  R  R = H;D03A  J  taci  , ,. . , . poly(iminocarboxylate)  Chart 3.1.  In the development of MRI agents, some multinuclear Ln(III) complexes have been found. In the attempt to grow crystals of Gd(D03A) (D03A = l,4,7-tris(carboxymethyl)1,4,7,10-tetraazacyclododecane),  Chang  et  al.  1 9  reported  a  trimeric  [{Gd(D03A)}3.Na C03].17H 0 structure, in which three mononuclear Gd(D03A) units 2  2  were linked together by one carbonate through two oxygen atoms bound to each Gd. Hegetschweiler and co-workers discovered sandwich-type cage structures of trinuclear 30  [M (H_3L) ] complexes [M = La, Gd and L = l^^-triamino-l^^-trideoxy-cw-inositol 3+  3  2  (taci)] which are composed of three Ln(III) ions, two triply deprotonated taci ligands with bridging alkoxo groups, and chloride anions and/or water molecules to complete the  - 44 -  References on p. 83  Chapter 3  coordination spheres. Other examples of multinuclear Ln(III) complexes of MRI interest were those with tripodal poly(iminocarboxylate) in which carboxylate pendant arms formed bridges.  31  The results with the ligands from other groups described above,  21-28  '  30  and with  multidentate ligands from our laboratory ' suggested to us the construction of multinuclear 18 20  lanthanide and mixed lanthanide/transition metal ion arrays. The latter is elaborated upon in the aggregation of and interaction among Ln(III) and 3d-metal ions.  32  In this chapter, the  syntheses and characterization of Ln(III) complexes containing deprotonated rkbbpen (N,N'bis(2-hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine, H2LI), HClbbpen (N,N'2  bis(5-chloro-2-hydroxybenzyl)-N,N' -bis(2-methylpyridyl)ethylenediamine,  H2L2),  and  H^Brbbpen (N,N'-bis(5-bromo-2-hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine, H2L3) will be discussed.  Z = H,H bbpen(H Ll) = CI, H Clbbpen (H L2) = Br, H Brbbpen (H L3) 2  2  2  2  Three types of complexes were synthesized: monocationic  dinuclear  ([Ln2L2(N03)] ) +  2  2  neutral mononuclear ([LnL(N03)]), and  monocationic  trinuclear  ([Ln L (X) (CH OH)] ) species, where X = bridging (CH3COO") and bidentate ligands (N0 " +  3  2  n  3  3  CH3COO", CIO4'), and n is 4. The factors that control the types of complexes formed are the  size of Ln(III) ions and the base used in the reaction. Sodium hydroxide with small Ln(III) ions (Dy-Lu) resulted in [LnL(N03)] complexes; while, the same base with larger Ln(III) ions (La-Gd) produced [Ln2L2(N03)] complexes. Similar reactions in the presence of +  -45-  References on p. 83  Chapter 3  acetate, replacing hydroxide, resulted in the formation of [Ln3L2(X) (CH30H)] complexes in +  n  which acetate anions and ligand phenolate oxygen atoms acted as bridges among three Ln(III) units. In a very simple one step reaction, [LnL(NC»3)] and [Ln L (N03)] complexes +  2  2  (which are insoluble in methanol) can be converted to [Ln3L2(X) (CH30H)] complexes n  +  which are very soluble in methanol. The coordination number of Ln(III) in these complexes varies from seven to ten. The pro-ligands reported herein (H2LI-H2L3) are potentially hexadentate and clearly do not satisfy the coordination number requirement of Ln(III) ions.  The mismatch of ligand  denticity with Ln(III) coordination numbers can be utilized specifically to create multinuclear species with or without additional small bridging ligands.  3.2. Experimental Materials.  Hydrated lanthanide salts, ethylenediamine, salicylaldehyde, sodium  borohydride, 2-picolylchloride hydrochloride, hexadecyltrimethylammonium bromide, sodium hexafluorophosphate, sodium perchlorate and anhydrous sodium acetate were obtained from Aldrich or Alfa and were used without further purification. N,N'Bis(salicylidene)ethylenediamine  (H salen),  N,N' -bis(2-hydroxybenzyl)ethylenediamine  33  2  (H bben), N,N'-bis(2-hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine (H bbpen, 2  2  H L1),  N,N'-bis(5-chloro-2-hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine  2  (H Clbbpen, 2  H L2), 2  and  N,N'-bis(5-bromo-2-hydroxybenzyl)-N,N'-bis(2-  methylpyridyl)ethylenediamine (H Brbbpen, H L3) were all prepared as described in the 2  2  literature.  34  -46-  References on p. 83  Chapter 3  Instrumentation.  Mass spectra (Cs , LSIMS (Liquid Secondary Ion Mass +  Spectrometry)) were obtained on a Kratos Concept II H32Q with thioglycerol as the matrix. The uncertainty of m/z in the LSIMS is ± 1. Infrared (IR) spectra were recorded as KBr discs in the range 4000-500 cm" on a Galaxy Series 5000 FTIR spectrometer (with an uncertainty 1  of ± 4 cm"). C, H, N and CI analyses (with uncertainties of ± 0.3%) were performed by Mr. 1  Peter Borda in this department.  Room temperature magnetic susceptibilities of some  lanthanide complexes were measured on Johnson Matthey magnetic susceptibility balance using Hg[Co(NCS)4] as the susceptibility standard. Syntheses of metal complexes. The preparations of mononuclear ([LnL(NOa)]) and dinuclear ([Ln2L2(N03)]N03) complexes were similar; thus, detailed procedures are given for representative examples, and all compounds prepared, along with their characterization data are listed in Tables 3.3, 3.4, and 3.5 on p. 55, 58, and 59, respectively. N. B. It should be noted that perchlorate salts of metal complexes are potentially explosive and should be handled with care.  [Ln(Ll)N0 ]. mH 0. (Ln=Dy) To a methanolic solution of H L1 (0.093 g, 0.20 mmol) 3  2  2  and 50 pL of 8 M NaOH (0.4 mmol), a methanolic solution of Dy(N0 ) .5H 0 (0.087 g, 3  3  2  0.20 mmol) was added. The mixture was stirred at room temperature for 1 h. The resulting precipitate was collected by vacuum filtration and dried in air: yield 103 mg (75%). Yields for the other mononuclear complexes: Er, 88%; Yb, 81%; Lu, 91%. [Ln2(Ll)2(N03)] NO3. mH20.  These complexes were prepared similarly to the  mononuclear Dy-Lu complexes. Yields for the dinuclear complexes: La, 63%; Pr, 88%; Sm, 64%; Gd, 86%.  -47-  References on p. 83  Chapter 3  General preparative method for trinuclear ([Ln3L2(X)„(CH30H)] Y, where Y=counter anion) complexes (details provided in Table 3.2). Table 3.2. Preparative Details for the Trinuclear ([Ln L2(X) (CH OH)] Y) Complexes. 3  Ln(III)-salt starting material Pr(N0 ) .6H 0 3 3  2  Pro-ligand H L1 2  n  3  Counter Product anion salt added none [Pr (Ll) (CH COO) (N0 ) (CH OH)] 3  2  3  2  3 2  3  Yield 25%  N0 »5H 0 3  Sm(N0 ) .6H 0 3 3  2  H L1 2  2  [Sm (Ll) (CH COO) (N0 ) CH OH]  none  3  2  3  2  3 2  3  35%  N0 »CH OH»5H 0 3  Gd(N0 ) .6H 0 3 3  2  H L1 2  3  2  [Gd (Ll) (CH COO) (N0 ) (CH OH)]  none  3  2  3  2  3 2  3  29%  N0 «2H 0 3  Gd(N0 ) .6H 0 3 3  2  H L1 2  2  [Gd (Ll) (CH COO) (N0 ) (CH OH)]  NaPF  3  6  2  3  2  3 2  3  39%  PF »H 0 6  GdCl .6H 0 3  H L3  2  2  NaClC>4  2  [Gd (L3) (CH COO) (CH OH)] 3  2  3  4  48% *  3  ClCvfbO Ho(C10 ) .6H 0 4 3  2  H L2 2  [Ho (L2) (CH COO) (C10 )(CH OH)]  none  3  2  3  3  4  3  73%  ClCyH 0 2  H L1  YbCl .6H 0 3  2  2  NaC10  4  [Yb (L 1 ) (CH COO) (C10 )(CH OH)] 3  cio Lu(N0 ) .6H 0 3 3  2  H L1 2  none  2  3  3  4  3  25%  4  [Lu (Ll) (CH COO) (N0 )(CH OH)] 3  2  3  3  3  3  17% *  N0 »2H 0 3  2  *Product after recrystallizationfromhot methanol  To a suspension of 0.2 mmol of H2L and 0.5 mmol of anhydrous sodium acetate (NaCH COO) in 10 mL methanol, 0.2 mmol of lanthanide salt was added. The mixture was 3  stirred for 1 hr at room temperature. The mixture was filtered and in some cases, a counter anion salt was added to the filtrate. The filtrate was left at room temperature for slow evaporation, or in the refrigerator. The product was collected by vacuum filtration and dried in air. Suitable crystals of the trinuclear complexes (Ln=Sm and Gd) were obtained from  -48-  References on p. 83  Chapter 3  slow evaporation at room temperature and recrystallization from methanol, respectively, and were used in X-ray diffraction studies (vide infra).  General preparative method for the conversion of [LnLfNOa)] or [Ln L2(N03)]N03 to 2  [Ln3L2(X)„(CH30H)]Y complexes (see Scheme 3.2 on p. 51). To a suspension of [Gd (Ll) (N0 )] N 0 ' 3 H 0 (420 mg, 0.30 mmol) in methanol, 2  2  3  3  2  Gd(N03)3.6H20 (140 mg, 0.31 mmol) and sodium acetate (55 mg, 0.67 mmol) were added; the initial solution was cloudy white. While being stirred for 1 h at room temperature, the suspension became clear. The solution was filtered, and the filtrate was left at room temperature for slow evaporation. The white precipitate (300 mg, 58% yield) was collected via vacuum filtration and dried in air. Similar procedures were followed for Pr and Lu; yields were 25% and 20%, respectively. IR, elemental analyses and mass spectra showed that the resulting products have the general formula [Ln (Ll)2(CH COO)2(N03)2(CH30H)] 3  NO3. mH 0.  3  The same complexes can also be obtained from the reaction of  2  [Gd (Ll) (N0 )] N 0 and Gd(CH COO) or from the reaction of [Gd (Ll) (N0 )] N 0 , 2  2  3  GdCl3.6Ff.2O  3  3  3  2  2  3  3  and sodium acetate.  All complexes have been characterized by IR spectroscopy (Table 3.3 on p. 55), mass spectrometry (Table 3.4 on p. 58), elemental analysis (Table 3.5 on p. 59) and in some cases by X-ray crystallography.  X-ray Crystallographic Analyses.  All crystal structures in this chapter were  determined by the late Dr. Steven J. Rettig of the UBC structural chemistry laboratory. ORTEP  drawings  of  the  mononuclear  -49-  [Yb(Ll)(N03)J,  of  the  dinuclear  References on p. 83  Chapter 3  [Pr (Ll)2(N03)(H 0)] cation in [Pr (Ll) (N0 )(H 0)]N0 »CH OH, of the dinuclear +  2  2  [Gd (Ll) (N0 )] 2  2  +  3  2  2  3  2  3  3  cation in [Gd (Ll) (N0 )]N0 »CH OH«3H 0, 2  2  3  3  3  2  of the trinuclear  [Gd (L3) (CH COO) (CH OH)] cation in [Gd (L3) (CH COO) (CH OH)]C104«5CH OH, +  3  and  2  of  3  the  4  3  3  trinuclear  2  3  4  3  3  [Sm (Ll) (CH COO) (N0 ) (CH OH)]  +  3  2  3  2  3  2  3  cation  in  [Sm (Ll) (CH3COO)2(N03) (CH OH)]N03»CH OH»3.65H 0 are shown in Figures 3.3 to 3  2  2  3  3  2  3.7, respectively. Selected bond lengths and bond angles are listed in Tables 3.6 to 3.10. Selected crystallographic data are presented in Table A7 (Appendix).  3.3. Results and Discussion The complexation of LI " (bbpen"), L2 " (Clbbpen") and L3 " (Brbbpen") with 2  2  2  2  2  2  lanthanide(III) (Ln(III)) ions results in three types of complexes depending on the base used in the reactions and on the size of Ln(III) (see Scheme 3.2). When two equivalents of sodium hydroxide (NaOH) were used as a base with one equivalent each of Ln(III) salt and H L, 2  smaller Ln(III) ions (Dy-Lu) formed neutral mononuclear complexes ([LnL(N0 )]) 3  containing one Ln(III), one ligand and one bidentate nitrate in their coordination spheres. When similar reactions were performed with larger Ln(III) ions (La-Gd), monocationic dinuclear complexes ([Ln L (N0 )] ) were produced. These contain two Ln(III), two L " +  2  2  2  3  ligands with bridging phenolate oxygen atoms, and one bidentate nitrate. Some complexes contained water molecules in their coordination spheres.  -50-  References on p. 83  Chapter 3  Chapter 3  The third type of complex was formed when the same reactions were carried out with at least two equivalents of sodium acetate as a base.  Monocationic trinuclear complexes  ([Ln L (X) (CH OH)] , where X = bridging (CH COO") and bidentate ligands (N0 ", +  3  2  n  3  3  3  CH COO", CIO4"), and n is 4) were produced in this case. They are composed of three 3  Ln(III), two ligands with bridging phenolate oxygen atoms, bridging (and/or bidentate) acetates and bidentate nitrates. The [LnL(N0 )] and [Ln2L2(N0 )]N0 complexes can be easily converted to 3  3  3  [Ln L2(X) (CH OH)]Y complexes by adding 2-3 equivalents of sodium acetate and one 3  n  3  equivalent of Ln(III) salt (Ln(N0 ) or LnCl ) or just by adding one equivalent of a 3  3  3  lanthanide acetate salt (Scheme 3.2). Based on IR, mass spectra and elemental analyses, the resulting [Ln L (X) (CH OH)]Y complexes have the same formulation as that produced in 3  2  n  3  the reactions of one equivalent of Ln(III) salts, one equivalent of pro-ligand and 2-3 equivalents of sodium acetate, as summarized in Table 3.2 on p. 48. The conversion to [Ln L2(X) (CH OH)]Y complexes is only successful when acetate anion is present. Other 3  n  3  potentially bridging anions (nitrate and perchlorate) have been used in attempts to construct [Ln L (X) (CH OH)]Y complexes from [LnL(N0 )] or [Ln L (N0 )]N0 ; however, these 3  2  n  3  3  2  2  3  3  reactions were not successful. When Ln(N0 ) and two equivalents of sodium acetate were 3  3  used in this conversion, nitrate was the counter anion of the complex cation (i.e. Y=N0 ). If 3  LnCl was used instead of the nitrate salt, the counter anion of the complex cation was 3  chloride (Y=C1). If a lanthanide acetate salt was utilized, the counter anion of the product was nitrate (Y=N0 ). The mechanism of this interconversion has not yet been studied; it 3  possibly, however, involves rearrangement of each unit instead of simply the insertion of the middle Ln unit.  -52-  References on p. 83  Chapter 3  1500  1400  1300  1200  Figure 3.1. IR bands (1520-1200 cm") of all mononuclear [LnL(N0 )] (Ln=Dy-Lu) and 1  3  dinuclear [Ln2L2(N03)]N03 (Ln=La-Gd) complexes. T, bidentate nitrate stretching bands; 8, C-0 deformation bands of bridging phenolate; •, free (uncoordinated) nitrate stretching bands.  -53 -  References on p. 83  Chapter 3  Selected IR stretching frequencies of all complexes are listed in Table 3.3. The [LnL(NC»3)] complexes show stretching frequencies typical of bidentate nitrates (1480 and 1300 cm"). However, they lack the strong stretching bands of free (non-coordinated) anionic 1  nitrate (Figure 3.1); instead, they exhibit weaker bands due to the ligands around 1385 cm". 1  Due to the overlapping ligand and free nitrate bands, IR spectra alone are not an adequate tool to indicate the absence of free nitrates in the mononuclear complexes.  The  [Ln2L2(N03)]NC»3 complexes show both bidentate nitrate bands (1480 and 1290 cm") and a 1  free anionic nitrate band at 1384 cm" (Figure 3.1). 1  Both the former and the latter are  consistent with the literature values reported for [La(N03)3(phen)2].  35  Another significant difference between the [LnL(NC>3)] and [Ln2L2(NC»3)]N03 complexes is the presence of a band at 1260 cm" in the latter (Figure 3.1), possibly a 1  deformation band in a bridging phenolate group. A characteristically strong deformation band of the phenolato ligand is found in phenoxide erbium complexes, where it appears at 1270 cm" .  1 36  The deformation band of non bridging phenolates in the [LnL(NC»3)]  complexes overlaps with the lower frequency band of the bridging nitrate resulting in a strong broad band around 1300 cm". 1  The trinuclear complexes ([Ln3L2(X) (CH30H)]Y) have more complicated infrared n  stretching vibrations because of the presence of bridging phenolates, free anionic nitrate, free hexafluorophosphate, or free perchlorate counter anion (Y), bridging acetates and bidentate acetates or nitrates in some cases. The nitrate bands (bidentate and anionic) appear at the same frequencies as in the [LriL(NC>3)] and [Ln L (N03)]N0 complexes. 2  -54-  2  3  References on p. 83  Chapter 3  g  c u -a  "ST  ^1" 1—H  60  s  ro  ^H  rN  VO  m  m  in  1—1  o O u  o m  >n  ft  rN in in  in in  CN ro <n  in  ro  VO  CN  CN  i^-H —H  "5b  -a  m  •ST" VD  in  r—'  ro  o"  m  >n  VO  m  I^—HH Tl-  Tf  ^H  VO  VO  CN  ro vo CN  r~in CN  O  o  o  CJ  u  in  1—1  oo T3  S  — vo CN  -4—»  O vo CN  O VO CN  ON m CN  oo  ON  00 00 CN  o  CN  o  CN  CN  ro  #  *r0o0  m CN  o  VO rN  oo IT)  CN  r-  m CN  ON  in rN  "o  a  -J 1)  J3  a. 00  ON  CN  o o ro  o o ro  CN o ro  00  OO  CN  00 CN  00 CN  ON  ON  „  "2 3  E o  *O0 0  #  ON  *0 0 TT  *0 0  *ON  *oo o  TT  *o0 0  "3-  *0 0  *0r-H0  CN  OO •3-  ON  # in 00  00  (/) Tt  "3 c u  -  m  CO  OO  ro  ro  ro 00 ro  rj00  OO  ro  in 00 ro  in 00 ro  CN  OH PH  u  CO  ro  Tf  ^3  00  PH  o  CN  o  ON  o  ON  o  Mil S  *c ffl  in  o  a  O'  u o  <  in •  u  i  Z o Q  1  O  o  fN ro  CM  O  X  TD U  z  OS  c  O  u "a. — E o H  o z /•—\ a X o o m X a u CJ fN o m o z  of  CS  a  CJ  z  o  g  d  2  Q  w  O  z  O  9  o z o  Q, CN  o z O  O  a ro m  o z  O  fN  o o o  m  CJ  z  3  O  2  d  £•  E  fN  o o u a o  a CN  o z a o  m  X  U  PH  (/3  a CN  o z a o a  CJ  6 d  4 & o o  CJ  a  T3  T3  -55-  (N  o  o o  CJ  a  3 h-1  a  u* CU  X o a o  o o o o o  T3  o  O  o  o  a o  a o a"  a o o a o a-  CO  a CJ  CJ  CJ  CJ  o o  o o o  6  o  CJ  CJ  m  X  o  o  a  u  CJ  ro  CN  T3  o  a  o a  CJ  ^  References on p. 83  Chapter 3  The deformation bands of bridging phenolates are also as observed in the latter complexes. In the cases where acetate is present as a bridging ligand, vcoo appears around 1560 and 1412 cm", a frequency difference of approximately 150 cm". In other cases where acetate is 1  1  also present as a bidentate chelating ligand, vcoo" appears at around 1530-1550 and 1450 cm". The frequency difference between these two bands (~ 100 cm") is smaller than that in 1  1  bridging acetate, consistent with the literature.  37  The LSIMS spectra of all complexes were obtained in a thioglycerol matrix in the positive ion detection mode. The complete results are presented in Table 3.4. [LnL(NC>3)] complexes,  [LnL]  +  In the  parent peaks are observed, as they are in the  [Ln2L2(N03)]N0 complexes. In addition to [LnL] , [Ln L (N03)] peaks are also present in +  +  3  2  2  the latter. These peaks, along with the presence of C-0 bridiging phenolate deformation bands in the IR (vide supra), were used to confirm the dinuclearity of these complexes. Generally, the spectra of the [Ln3L2(X) (CH30H)]Y complexes show parent peaks of intact n  monocationic [Ln L2(CH COO)2(N03)2] 3  +  3  and of [Ln L(CH COO)2(N03)]  +  2  3  and [LnL]  +  fragments (Figure 3.2). The detection of intact high molecular weight parent peaks in the mass spectra suggests strongly the stability of these trinuclear molecules. The magnetic susceptibilities of some complexes were measured at room temperature 1/2  (Table 3.5). They are similar to those of the calculated pff values (pff = g [J(J+1)] ). In e  e  general, the Ln(III) ions are magnetically dilute (not interacting); a very weak exchange (-J = 0.045 cm") was found in an encapsulated dimer of aminephenolato Gd(III) complex. 1  38  -56-  References on p. 83  Chapter 3  610  948  1619  m/z  Figure 3.2.  Mass spectrum of trinuclear [Gd3(Ll)2(CH3COO)2(N03)2(CH OH)]N03 3  showing the experimental (lower) and simulated (upper) isotopic patterns for major peaks.  -57-  References on p. 83  Chapter 3  O  © CN CN  2  ' < CJ  .  VO m  2  s  d eS  o  ©_ o  ©^ CN  CN  rvf  oC  o ^ Ov in  of  oo vo vo  CN Ov  vo  +  ©^  T  =: CJ  o  eS  CN  CN  CN  Ov  m m Ov  m ov m  o vo  o  ©^  vo CN vo  CN VO  cP cr in of rrov Ov  CN oo"  •* Ov  CN 00 CN  CN  15. vo  —i  VO  O CN VO  vo CN VO  CN  VO  Ov m  m  Ov in  o  ~H  O VO  vo  o — H vo  o ^ vo  oo VO r-  in oo vo  X m  O ro  X in  o  CN  a  a a o o o CoN a z a X a o o o o o X a CJ CJ a o a a o o CJ B CJ CJ O o o O o o o O o CJ CJ  o PH z GH a a o o o o a X X U u CJ cj O o g o & & o o o o o o o o o CJ CJ c j CJ CJ a a a CJ a o CJ o K CJ CJ CJ a a CO CN o ro  ro  ro  ro  ro  ro  co  o  ro  X in  o •  $  6  d  2 d  Q  W  6  z § z z  "a, S i  6  ro  ro  CN  6  o o X o X a CN CN a o o o o z z z z 2 o 9 o ^  -i 3  h-1  —  C/3  o  -58-  /  s  ro  vS  m  fN  to  v S co  co  en  co  1  1  e  /•—\  co  —  1  C/5  ro  co  co  -H  hJ  HJ  T3  TD  o o  ro  O  o  3  a References on p. 83  Chapter 3  Tf Tf  4) o 00  m  CQ IB  Tf T£  60 cS  60 cS  am  -H  am  Tf  o  "3  •5  o  VO  Tf  o  in rn en  NO  o ©  o  o-H  -H  -—  O  Tf  Tf  m  00  in 00  ON  ON  ON,  £H  r(N O  in  NO  o  ©  rm o  CN  m m  o  m  Tf Tf' T Tff Tf' Tf Tf Tf' Tf' Tf CN  p-  O CN o CN  Tf  o  ON  o  VO  ON ON  ON  00  00  m . rn  00 CN 00  r~  00 in ON  Tf Tf Tf Tf  rvo  ON  CN O  ON  Tf  ON  00  Tf Tf Tf Tf  CN  ON  ON  ON  ON  VO ©' in  ,  O  2 2  m in  O rn  o  00 CN  m  m  ON  ON  00  Tf Tf T^f Tf Tf Tf Tf  t~- 0 0 CN t> o ON >n  00  ON  00  m  CN  ON  T£  CN  00  V  oo  CN  Tf' Tf' Tf' Tf' T Tff Tf' T Tff T Tff'  /  oo" vo 00 00  00 in  ON  ON  CN  vo  Tf  Tf  vo  o  £  ON  00  NO ON  60  -H  oo  ON  ON  o  -H  CN  j  00 m  m  Tf  m  T Tff Tf' rm  in  t-; Tf  Tf Tf  ON  00  00 00  m  ON  1  in  Tf CN r-;  cn in  0  s  VO  in  ,  ^ in  VO  O  r^  NO^  CN  ON  ^  — :  o 0 0  oo ^  rn in  in  O  00  in  T f' T f T Tff T"l'  rn  rn  m vq rn  O  cn 00  O  ON  rn  rn  o 00 rn  r~ VO O  r-  ON  ON  r-~ rn 00 m  CN rn  TI-  ON  m in 00 m  o rn  o  ON  cn  CN O  Tf Tf Tf Tf T—H r-;  CN"  CS  00  TT  ON  cn  o  TT  -: vo  TT. Tf T Tff  Tf c-^ m  rin m  r-i —  O  r-  ON  rn  o  Tf TICS CN  Tf Tf >  "**^  VO  o  CN  Tf Tf  o a m a o o a o x a m CoN a• m o a o o o a z z o a a o" ' aG oa a o • o o u o o CJ mo a CJ a a m z a CJ a a o o o o o a 2 o m & 5, o o CJ a o o o o o o o O o o o o o o o o  a CN o z a o a  ma a a a a a o a O CJ CJ CJ CJ  a-  fN  fN  fN  TT  Tf  PH  Tt  ro  Q, o *  o IT)  2  o |CJ  g  m  z z 2 o  ©  r5  x  CN O 2 o z z o  X  m o  m  mm o o  Z  Z  d  J  fN  fN  o  O  ro  CJ  ro  CJ  ro  o  (N  eel hJ  ro  t-7 PH  T3  00  O -59-  CJ  ro  -O  ro  CN  m  T3  CJ  d d ro  ro  uCJ  ro  ro  CJ  ro  O ro O O CJ  ro  o  <—i  d ro  -a o .o  s  o aReferences >H on p. 83  Chapter 3  The X-ray structural analysis (Figure 3.3) shows that mononuclear [Yb(Ll)N03] consists of one Yb atom, one hexadentate LI " and one bidentate nitrate. This molecule has a C2 axis, and the coordination number of Yb(III) is eight. The coordination geometry around Yb can be best described as a distorted dodecahedron (Figure 3.3). The hexadentate ligand LI forms a "cap" around Yb(III) with an 0(1)-Yb-0(1*) angle of 156.3° and an N(2)-Yb2-  N(2*) angle of 155.5°. Complexes of Ga(III) and In(III) with hexadentate L2 ' exhibit 2  octahedral geometry around the metal centers, with a greater degree of distortion in the latter. The cavity around hexadentate LI is too small to completely encapsulate a larger 34  2-  Yb(III) ion; thus, along with a bidentate nitrate to satisfy a higher coordination number of 3  Yb(III), L I forms a dodecahedral geometry around the central metal ion. Kepert 2-  39  41  predicted that the dodecahedral geometry should be significantly stabilized relative to the square antiprismatic geometry for small "bite" ligands, such as bidentate nitrate. Selected bond lengths and bond angles are presented in Table 3.6. The average Yb-N bond length is 2.506 A, similar to an eight coordinate Yb complex (Yb-N (average) 2.52 A), and a seven coordinate Yb amine phenolate complex (Yb-N (avg) 2.497 A). 42  43  The  Yb-0(phenolate) bond length is 2.163(4) A which is similar to that reported by Yang et al. (Yb-0 (avg) 2.158 A)  4 3  The Yb-O(nitrate) (Yb(l)-0(2) = 2.432 A) bond length is similar  to that of ten-coordinated K [Er(N0 )5] which has an average Yb-O(nitrate) value of 2.431 2  A  4 4  3  The 0(2)-N(3)-0(2)* angle is 116.8°, smaller than that in unbound nitrate (120°). In  fact, this is true for all the bidentate nitrates in all the structures reported herein. This is consistent with O-N-0 angles of bidentate nitrate in trinitrato-l,2-bis(pyridine-2aldimino)ethanegadolinium(III), ranging from 115.1° to 117.4°.  -60-  45  References on p. 83  Chapter 3  Figure 3.3. ORTEP diagram of [Yb(Ll)] NO3 and a scheme of the coordination geometry around Yb(III), shown with the same numbering as the crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 33% probability level. -61 -  References on p. 83  Chapter 3  Table 3.6. Selected Bond Lengths (A) and Bond Angles (deg) in [Yb(Ll)N0 ]. 3  Yb(l)-0(1)  2.163(4)  Yb(l)-N(l)  2.504(4)  Yb(l)-0(2)  2.432(4)  Yb(l)-N(2)  2.508(4)  0(1)-Yb(l)-0(1*)  156.3(2)  0(2)-Yb(l)-N(l)  141.15(14)  0(l)-Yb(l)-0(2)  128.19(14)  0(2)-Yb(l)-N(l*)  132.40(14)  0(l)-Yb(l)-0(2*)  75.49(14)  0(2)-Yb(l)-N(2)  79.17(15)  0(1)-Yb(l)-N(l)  77.65(14)  0(2)-Yb(l)-N(2*)  78.93(15)  0(1)-Yb(l)-N(l*)  83.11(14)  N(l)-Yb(l)-N(l*)  71.4(2)  0(1)-Yb(l)-N(2)  98.78(15)  N(l)-Yb(l)-N(2)  67.26(15)  0(1)-Yb(l)-N(2*)  86.25(14)  N(l)-Yb(l)-N(2*)  137.01(15)  0(2)-Yb(l)-0(2*)  53.1(2)  N(2)-Yb(l)-N(2*)  155.5(2)  •symmetry operation: 1-x, y, 'A-z  The structural analysis of dinuclear [Pr2(Ll)2(N0 )(H 0)][N03] (Figure 3.4) shows 3  2  the presence of two praseodymium atoms (Pr(l) and Pr(2)), one hexadentate ligand (LI ") with only terminal phenolate oxygen atoms (0(1) and (0(2)), another L I  2-  with two  phenolate oxygen atoms (0(3) and 0(4)) bridging between Pr(l) and Pr(2), and one bidentate nitrate bound at Pr(2). Thus, the coordination numbers of Pr(l) and Pr(2) are eight and nine, respectively.  The geometry around Pr(l) is best described as a distorted cube, while the  geometry around Pr(2) is closest to a monocapped square antiprism, with coplanar 0(3), 0(4), N(5) and N(6) forming one square face and coplanar 0(6), 0(8), N(7) and N(8) forming the other square face with 0(5) as a cap (Figure 3.4). The cubic geometry around Pr(l) is one of a few rare examples of cubic Ln(III) complexes. ' " 26 46  molecular orbital analysis by Hoffmann and co-workers  46  - 62 -  50  A theoretical  determined that the cubic References on p. 83  Chapter 3  geometry is less stable than the more common dodecahedron, square antiprism or bicapped trigonal prism due to electronic and steric effects. The monocapped square antiprismatic geometry around Pr(2) is a common coordination geometry for complexes with coordination number of nine. In fact, all structures with a coordination number of nine reported herein have the same type of geometry, with the exception of the geometry around Gd(2) in the dinuclear [Gd2(Ll)2(NC»3)]  +  (vide infra).  Selected bond lengths and bond angles are listed in Table 3.7. The average bond length of terminal oxygen atoms to Pr(l) (Pr(l)-0(1) and Pr(l)-0(2)) is 2.335 A. This value is similar to a six-coordinate Pr-0(terminal phenolate) average bond length of 2.341 A.  51  Since the bridging oxygen atoms (0(3) and 0(4)) form two strong Pr-0 bonds, their basicity should be lowered relative to that of singly bonded O atoms; the bridging Pr-0 distance (average of 2.434 A) is 0.08 A lower than Pr-O(terminal) distance, as expected. The angles at the phenolate oxygen bridgeheads are 113.71(7)° (0(3)) and 109.31(7)° (0(4)). The distance between the two metal centers (Pr(l)-Pr(2)) is 4.022 A. The bond length of Prostrate) is 2.588 A, slightly lower than that found in a phenolate Schiff base complex of praseodymium. The Pr-O(water) bond length (2.448 A) is similar to that of Kahwa et al. 52  (2.535 A). The average Pr-N bond length is 2.706 A, shorter than the expected Pr-N 53  distance based on Gd-N bond length (2.695 A average) after correcting for the difference 51  of ionic radii between the two metal ions.  3  -63-  References on p. 83  Chapter 3  Figure 3.4. ORTEP diagram of the [Pr (Ll)2(N03)(H 0)] cation in [Pr (Ll) (N03)(H 0)] +  2  2  2  2  2  N0 «CH OH, and a scheme of the coordination geometries around each Pr(UI) center, 3  3  shown with the same numbering as the crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 33% probability level, and some of the phenolate and pyridyl ring atoms have been omitted for clarity.  -64-  References on p. 83  Chapter 3  Table 3.7. Selected Bond Lengths (A) and Bond Angles (deg) in the Cation of [Pr (Ll)2(N03)(H 0)] [NO3KH3OH. 2  2  Pr(l)-Pr(2)  4.022(7)  Pr(2)-0(3)  2.377(2)  Pr(lMXl)  2.309(2)  Pr(2)-0(4)  2.448(2)  Pr(l)-0(2)  2.400(2)  Pr(2)-0(5)  2.588(2)  Pr(l)-0(3)  2.426(2)  Pr(2)-0(6)  2.588(2)  Pr(l)-0(4)  2.483(2)  Pr(2)-0(8)  2.448(2)  Pr(l)-N(l)  2.720(2)  Pr(2)-N(5)  2.712(2)  Pr(l)-N(2)  2.796(2)  Pr(2)-N(6)  2.717(3)  Pr(l)-N(3)  2.690(2)  Pr(2)-N(7)  2.643(2)  Pr(l)-N(4)  2.717(2)  Pr(2)-N(8)  2.652(3)  0(l)-Pr(l)-0(2)  165.92(7)  0(3)-Pr(2)-N(5)  72.29(6)  0(l)-Pr(l)-0(3)  93.70(6)  0(3)-Pr(2)-N(6)  104.51(7)  0(l)-Pr(l)-0(4)  80.10(7)  0(3)-Pr(2)-N(7)  75.79(7)  0(1)-Pr(l)-N(l)  70.39(7)  0(3)-Pr(2)-N(8)  149.30(6)  0(1)-Pr(l)-N(2)  120.70(7)  0(4)-Pr(2>-0(5)  130.43(6)  0(1)-Pr(l)-N(3)  104.29(7)  0(4)-Pr(2)-0(6)  146.06(7)  0(1)-Pr(l)-N(4)  74.47(7)  0(4)-Pr(2)-0(8)  74.37(6)  0(2)-Pr(l)-0(3)  78.54(6)  0(4)-Pr(2)-N(5)  115.14(7)  0(2)-Pr(l)-0(4)  86.06(7)  0(4)-Pr(2)-N(6)  74.32(6)  0(2)-Pr(l)-N(l)  120.05(6)  0(4)-Pr(2)-N(7)  141.83(7)  0(2)-Pr(l)-N(2)  73.35(7)  0(4)-Pr(2)-N(8)  80.42(7)  0(2)-Pr(l)-N(3)  75.66(7)  0(5)-Pr(2)-0(6)  49.44(7)  0(2)-Pr(l)-N(4)  115.06(7)  0(5)-Pr(2)-0(8)  71.39(7)  0(3)-Pr(l)-0(4)  67.60(6)  0(5)-Pr(2)-N(5)  113.89(6)  0(3)-Pr(l)-N(l)  157.88(7)  0(5)-Pr(2)-N(6)  119.40(7)  0(3)-Pr(l)-N(2)  113.29(6)  0(5)-Pr(2)-N(7)  68.63(7)  0(3)-Pr(l)-N(3)  139.94(7)  0(5)-Pr(2)-N(8)  68.04(7)  0(3)-Pr(l)-N(4)  79.96(6)  0(6)-Pr(2)-0(8)  120.74(7)  -65-  References on p.  Chapter 3  Table 3.7. Continued. 0(4)-Pr(l)-N(l)  121.97(6)  0(6)-Pr(2)-N(5)  72.73(7)  0(4)-Pr(l)-N(2)  158.36(7)  0(6)-Pr(2)-N(6)  79.47(7)  0(4)-Pr(l)-N(3)  80.46(6)  0(6)-Pr(2)-N(7)  72.09(7)  0(4)-Pr(l)-N(4)  137.00(6)  0(6)-Pr(2)-N(8)  68.75(7)  N(l)-Pr(l)-N(2)  65.91(7)  0(8)-Pr(2)-N(5)  142.67(7)  N(l)-Pr(l)-N(3)  61.25(7)  0(8)-Pr(2)-N(6)  144.54(6)  N(l)-Pr(l)-N(4)  80.96(7)  0(8)-Pr(2)-N(7)  85.28(7)  N(2)-Pr(l)-N(3)  87.91(7)  0(8>-Pr(2)-N(8)  94.72(7)  N(2)-Pr(l)-N(4)  61.02(7)  N(5)-Pr(2)-N(6)  67.75(7)  N(3)-Pr(l)-N(4)  139.08(7)  N(5)-Pr(2)-N(7)  65.04(7)  0(3)-Pr(2)-0(4)  68.93(6)  N(5)-Pr(2)-N(8)  122.00(7)  0(3)-Pr(2)-0(5)  134.90(7)  N(6)-Pr(2)-N(7)  130.08(7)  0(3)-Pr(2)-0(6)  139.89(6)  N(6)-Pr(2)-N(8)  63.93(8)  0(3>-Pr(2)-0(8)  79.08(7)  N(7)-Pr(2)-N(8)  134.12(8)  Pr(l)-0(3)-Pr(2)  113.71(7)  Pr(l)-0(4)-Pr(2)  109.31(7)  The X-ray crystal structure of [Gd2(Ll) (N03)][N03] (Figure 3.5) shows a dinuclear 2  [Gd2L2(N0 )] unit different from its Pr congener in that three phenolate oxygen atoms +  3  bridge the two Gd atoms. Gd(l) is coordinated by hexadentate LI , in which there is one 2-  bridging phenolate oxygen (0(2)), and also by two bridging phenolate oxygen atoms from the second ligand (0(3) and 0(4)); thus, the coordination number of Gd(l) is eight. Gd(2) is coordinated to bridging phenolate oxygen (0(2)), the second hexadentate ligand with its two bridging phenolate oxygen atoms, and one bidentate nitrate. The coordination number of Gd(2) is nine. Figure 3.5 also shows the coordination polyhedron around each Gd(III) ion. The coordination geometry around Gd(l) is best described as a distorted square antiprism - 66 -  References on p. 83  Chapter 3  which consists of coplanar N(l), N(2), N(3) and 0(2) and a second coplanar set of N(4), O(l), 0(3), 0(4).  The geometry around Gd(2) can be described as a distorted tricapped  trigonal prism with 0(4), 0(6) and N(5) as the capping atoms.  Square antiprismatic  geometry is also well-known among eight-coordination structures.  The geometry around  46  Gd(l), with three bridging phenolate oxygen atoms and with an ionic radius between those of Yb(III) and Pr(III), seems to be the midpoint between the eight-coordination dodecahedron 3  [Yb(Ll)N0 ] and the cubic geometry around Pr(l) in [Pr (Ll)2(N03)(H 0)]  +  3  2  2  (vide supra).  The tricapped trigonal prism found around Gd(2) is common among nine-coordination structures.  54  Selected bond angles and bond lengths are summarized in Table 3.8. The Gd-N distances have an average of 2.636 A, consistent with that of an eight-coordinated dimeric amine phenol (N 0 ) complex of Gd(III) (2.69 A),  51  4  3  acylic Schiff base ligand (2.349 A).  23  and longer than that of Gd(III) with  The Gd-0(terminal phenolate) (Gd(l)-0(1)) distance  is 2.230 A, similar to those reported by Liu et al. (2.253 A) and Howell et al. (2.207 A). This Gd-0(terminal phenolate) is again shorter than the average Gd-0(bridging phenolate) of 2.412 A in [Gd (Ll) (N0 )] , consistent with the literature. ' +  2  2  23 51  3  The difference of 0.18 A  between the former and the latter is slightly larger than those of dimeric amine phenol (N40 ) 3  complex of Gd (0.13 A), and of a dimeric Gd-acyclic Schiff base complex (0.14 A). 38  23  The  angles at the phenolate oxygen bridgeheads are 100.03° (Gd(l)-0(2)-Gd(2)), 96.13° (Gd(l)0(3)-Gd(2)), and 97.28° (Gd(l)-0(4)-Gd(2)).  Smaller angles at the phenolate oxygen  bridgeheads compared to those of Liu et al. (113.12°) and Howell et al. (108.7 ), and the 0  23  steric hindrance related the three bridging phenolate oxygen atoms result in a closer distance between the two gadolinium centers and longer Gd-0(bridging phenolate) bond lengths.  - 67 -  References on p. 83  Chapter 3  Figure 3.5.  ORTEP diagram of the  [Gd (Ll) (N0 )]  +  2  2  3  cation in [Gd (Ll) (N0 )] 2  2  3  N0 »CH OH»3H 0 and a scheme of the coordination geometries around each Gd(IU) center, 3  3  2  shown with the same numbering as the crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 33% probability level, and some of the phenolate and pyridyl ring atoms have been omitted for clarity. -68-  References on p. 83  Chapter 3  The Gd(l)-Gd(2) separation in [Gd (Ll) (N0 )] is 3.636 A, shorter than 3.984 A in +  2  2  3  [Gd (N403) ], and 3.81 A reported by Howell et al. To our knowledge, this is the first 51  2  23  2  characterized dinuclear Ln(III) structure with three phenolate oxygen bridges between the two metal ions. The Gd-O(nitrate) bond lengths (Gd(2)-0(5) 2.481 A and Gd(2)-0(6) 2.507 A) are consistent with another eight-coordinated dimeric gadolinium imino phenolate complexes reported by Howell et al. (2.494 A).  23  Table 3.8. Selected Bond Lengths (A) and Bond Angles (deg) in the Cation of [Gd (L 1 ) (N0 )] [N0 ]«CH OH«3H 0. 2  2  3  3  3  2  Gd(l)-Gd(2)  3.6362(3)  Gd(2)-0(2)  2.336(3)  Gd(l)-0(1)  2.230(3)  Gd(2)-0(3)  2.361(3)  Gd(l)-0(2)  2.409(3)  Gd(2)-0(4)  2.467(3)  Gd(l)-0(3)  2.524(3)  Gd(2)-0(5)  2.481(3)  Gd(l)-0(4)  2.377(3)  Gd(2)-0(6)  2.507(3)  Gd(l)-N(l)  2.728(3)  Gd(2)-N(5)  2.586(3)  Gd(l)-N(2)  2.665(4)  Gd(2)-N(6)  2.697(4)  Gd(l)-N(3)  2.501(3)  Gd(2)-N(7)  2.654(4)  Gd(l)-N(4)  2.613(4)  Gd(2)-N(8)  2.647(4)  0(l)-Gd(l)-0(2)  142.16(11)  0(2)-Gd(2)-N(5)  153.16(11)  0(l)-Gd(l)-0(3)  85.07(10)  0(2)-Gd(2)-N(6)  131.99(12)  0(l)-Gd(l)-0(4)  123.91(10)  0(2)-Gd(2)-N(7)  99.30(10)  0(1)-Gd(l)-N(l)  74.06(11)  0(2)-Gd(2)-N(8)  84.85(11)  0(1)-Gd(l)-N(2)  136.18(11)  0(3)-Gd(2)-0(4)  66.45(10)  0(1)-Gd(l)-N(3)  78.38(11)  0(3)-Gd(2)-0(5)  139.22(11)  0(1)-Gd(l)-N(4)  85.25(12)  0(3)-Gd(2)-0(6)  122.31(10)  0(2)-Gd(l)-0(3)  69.37(9)  0(3)-Gd(2)-N(5)  80.66(11)  -69-  References on p. 83  Chapter 3  Table 3.8. Continued. 0(2)-Gd(l)-0(4)  70.59(9)  0(3)-Gd(2)-N(6)  118.50(11)  0(2>-Gd(l)-N(l)  116.16(10)  0(3)-Gd(2)-N(7)  71.67(11)  0(2)-Gd(l)-N(2)  75.81(11)  0(3)-Gd(2)-N(8)  151.45(11)  0(2)-Gd(l)-N(3)  74.79(11)  0(4)-Gd(2)-0(5)  148.95(10)  0(2)-Gd(l)-N(4)  132.33(11)  0(4)-Gd(2)-0(6)  139.50(9)  0(3)-Gd(l)-0(4)  65.28(10)  0(4)-Gd(2)-N(5)  105.92(10)  0(3)-Gd(l)-N(l)  150.48(10)  0(4)-Gd(2)-N(6)  73.59(11)  0(3)-Gd(l)-N(2)  138.37(10)  0(4)-Gd(2)-N(7)  138.10(11)  0(3)-Gd(l)-N(3)  91.01(11)  0(4)-Gd(2)-N(8)  89.07(11)  0(3)-Gd(l)-N(4)  126.64(10)  0(5)-Gd(2)-0(6)  51.88(9)  0(4)-Gd(l)-N(l)  144.12(11)  0(5)-Gd(2)-N(5)  70.92(11)  0(4)-Gd(l)-N(2)  82.31(10)  0(5)-Gd(2)-N(6)  76.99(11)  0(4)-Gd(l)-N(3)  143.11(11)  0(5)-Gd(2)-N(7)  70.09(11)  0(4)-Gd(l)-N(4)  77.73(10)  0(5)-Gd(2)-N(8)  68.99(12)  N(l)-Gd(l)-N(2)  66.91(11)  0(6)-Gd(2)-N(5)  114.44(11)  N(l)-Gd(l)-N(3)  64.81(11)  0(6)-Gd(2)-N(6)  118.60(11)  N(l)-Gd(l)-N(4)  72.99(10)  0(6)-Gd(2)-N(7)  67.31(11)  N(2)-Gd(l)-N(3)  101.37(11)  0(6)-Gd(2)-N(8)  67.26(11)  N(2)-Gd(l)-N(4)  65.25(11)  N(5)-Gd(2)-N(6)  67.53(12)  N(3)-Gd(l)-N(4)  137.43(11)  N(5)-Gd(2)-N(7)  65.10(11)  0(2)-Gd(2)-0(3)  73.47(10)  N(5)-Gd(2)-N(8)  121.95(11)  0(2)-Gd(2)-0(4)  70.26(9)  N(6)-Gd(2)-N(7)  128.70(11)  0(2)-Gd(2)-0(5)  126.3(29)  N(6)-Gd(2)-N(8)  63.87(11)  0(2)-Gd(2)-0(6)  75.10(10)  N(7)-Gd(2)-N(8)  131.44(12)  Gd(l)-0(2)-Gd(2)  100.03(10)  Gd(l)-0(3)-Gd(2)  96.13(10)  Gd(l)-0(4Hjd(2)  97.28(10)  -70-  References on p.  Chapter 3  The X-ray structural analysis of trinuclear [Gd (L3)2(CH3COO)4(CH OH)][C104] 3  3  (Figure 3.6) shows the presence of three Gd(III) ions, two L3 " ligands with all phenolate oxygen atoms forming bridges, one methanol molecule, two bidentate acetates, one bridging acetate in classical r| :r| :p fashion and another bridging (tridentate) acetate in the less 1  1  2  common rf'rn/ip fashion where one of the acetate oxygen atoms (09) is bound to two 2  Gd(III) centres (also see diagram on p. 73). The geometry around nine-coordinated Gd(l) is best described as a distorted monocapped square antiprism with 0(1), 0(2), N(l) and N(2) forming one square face and N(3), N(4), 0(5) and 0(8) forming the other square face with 0(7) as a cap (Figure 3.6). Gd(2) has eight oxygen atoms in its coordination sphere which can be described as a distorted bicapped trigonal prism of which 0(6) and 0(9) are the capping atoms (Figure 3.6). Gd(3) has a coordination number of nine, and its geometry can be described as a distorted monocapped square antiprism (Figure 3.6). Atoms 0(3), 0(4), N(5) and N(6) form a square face as do N(7), N(8), 0(9) and 0(12), with 0(13) as a capping atom. Thus, the coordination environment around Gd(3) is exactly the same as in Gd(l). Along with the dodecahedron and the square antiprism, the bicapped trigonal prism is also quite common in eight-coordination structures. Comparison between the geometries around Gd(2) in the trinuclear Gd(III) complex and Sm(2) in the trinuclear Sm(III) congener (vide infra) shows that the  second capping atom (0(9)) in the former is in just the right position  and distance for coordination with Gd(2). Meanwhile, such a bond is absent in the trinuclear Sm(III) complex due to the larger ionic radius of Sm(III).  3  This is consistent with the  literature stating that the bicapped trigonal prism is the halfway point between a sevencoordinate monocapped trigonal prism and a nine-coordinate tricapped trigonal prism.  46  -71 -  References on p. 83  Chapter 3  Figure 3.6.  ORTEP diagram of the  [Gd (L3) (CH COO) (CH OH)]  +  3  2  3  4  3  cation in  [Gd (L3) (CH3COO)4(CH30H)]C104»5CH OH and a scheme of the coordination geometries 3  2  3  around each Gd(III) center, shown with the same numbering as the crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 33% probability level, and some of the phenolate and pyridyl ring atoms have been omitted for clarity. -72-  References on p. 83  Chapter 3  Selected  bond  lengths  and  bond  angles  for  the  cation  in  [Gd (L3)2(CH3COO)4(CH OH)][C104] are summarized in Table 3.9. The average Gd-N 3  3  bond length is 2.613 A, similar to another nine-coordinate GdfNeCM] hexaazamacrocycle with four phenolate pendant arms (Gd-N(avg) 2.63 A).  55  The average Gd-0(bridging  phenolate) is 2.397 A, and the angles at 0(1), 0(2), 0(3) and 0(4) bridgeheads are 111.9°, 111.3°, 102.5°, 101.3° respectively. The Gd-Gd separations are 3.956 A (Gd(l)-Gd(2)) and 3.726 A (Gd(2)-Gd(3)). They are slightly shorter than the Gd-Gd separation in the Gd2[N40 ]2 dimer which contains only phenolate oxygen bridges (3.9841 A)  51  3  [Gd (CH COO) ] " which contains four acetate bridges (3.960 A). 2  2  3  27  8  and  The Gd-0(bidentate  acetate) bond lengths have an average of 2.490 A, and the average Gd-0(bridging acetate) is slightly shorter at 2.375 A.  The tridentate bridging phenolate oxygen (0(9)) has a  significantly shorter bond distance to Gd(3) (2.432 A) compared to the Gd(2)-0(9) bond distance of 2.735 A. All of those Gd-O(acetate) bond lengths are consistent with those  CH  Gd(2)  measured in  [Gd2(CH COO)8] ". 2  3  27  Gd(3)  Ouchi et  al.  2S  have reported tridentate acetate bridging to  several lanthanide metal ions where the bond length to one metal ion is shorter than the one to another metal ion. The Gd-0(CH OH) bond length is 2.486 A. 3  -73 -  References on p. 83  Chapter 3  Table 3.9. Selected Bond Lengths (A) and Bond Angles (deg) in the Cation of [Gd (L3)2(CH COO)4 (CH OH)][ClO ]«0.5CH OH. 3  3  3  4  3  Gd(l)-Gd(2)  3.956(17)  Gd(2)-Gd(3)  3.726(17)  Gd(l)-0(1)  2.424(5)  Gd(2)-0(6)  2.347(5)  Gd(l)-0(2)  2.450(5)  Gd(2)-0(9)  2.735(5)  Gd(l)-0(5)  2.336(5)  Gd(2)-O(10)  2.441(5)  Gd(l)-0(7)  2.503(6)  Gd(2)-0(11)  2.476(5)  Gd(l)-0(8)  2.487(5)  Gd(3)-0(3)  2.364(5)  Gd(l)-N(l)  2.643(6)  Gd(3)-0(4)  2.447(5)  Gd(l)-N(2)  2.659(7)  Gd(3)-0(9)  2.432(5)  Gd(l)-N(3)  2.577(7)  Gd(3)-0(12)  2.471(5)  Gd(l)-N(4)  2.593(6)  Gd(3)-0(13)  2.500(5)  Gd(2)-0(1)  2.350(4)  Gd(3)-N(5)  2.727(6)  Gd(2)-0(2)  2.342(5)  Gd(3)-N(6)  2.598(6)  Gd(2)-0(3)  2.413(5)  Gd(3)-N(7)  2.557(6)  Gd(2)-0(4)  2.371(5)  Gd(3)-N(8)  2.553(6)  0(l)-Gd(l)-0(2)  64.39(15)  0(3)-Gd(2)-0(6)  145.9(2)  0(l)-Gd(l)-0(5)  81.5(2)  0(3)-Gd(2)-0(9)  63.3(2)  0(l)-Gd(l)-0(7)  138.2(2)  O(3)-Gd(2)-O(10)  79.0(2)  0(l)-Gd(l)-0(8)  141.4(2)  0(3)-Gd(2)-0(ll)  129.8(2)  0(1)-Gd(l)-N(l)  74.3(2)  0(4)-Gd(2)-0(6)  86.8(2)  0(1)-Gd(l)-N(2)  101.9(2)  0(4)-Gd(2)-0(9)  68.3(2)  0(1)-Gd(l)-N(3)  77.6(2)  O(4)-Gd(2)-O(10)  118.4(2)  0(1)-Gd(l)-N(4)  144.6(2)  0(4)-Gd(2)-0(ll)  88.1(2)  0(2)-Gd(l)-0(5)  75.1(2)  0(6)-Gd(2)-0(9)  130.6(2)  0(2)-Gd(l)-0(7)  131.2(2)  O(6)-Gd(2)-O(10)  135.0(2)  0(2)-Gd(l)-0(8)  145.7(2)  0(6)-Gd(2)-0(ll)  70.6(2)  0(2)-Gd(l)-N(l)  114.7(2)  O(9)-Gd(2)-O(10)  50.2(2)  0(2Hjd(l)-N(2)  73.1(2)  0(9)-Gd(2)-0(ll)  66.8(2)  -74-  References on p.  Chapter 3  Table 3.9. Continued. 0(2)-Gd(l)-N(3)  138.6(2)  O(10)-Gd(2)-O(ll)  73.5(2)  0(2)-Gd(l>-N(4)  80.2(2)  0(3)-Gd(3)-0(4)  68.9(2)  0(5)-Gd(l)-0(7)  69.9(2)  0(3)-Gd(3)-0(9)  69.0(2)  0(5)-Gd(l>-0(8)  121.9(2)  0(3)-Gd(3)-0(12)  145.4(2)  0(5)-Gd(l)-N(l)  145.0(2)  0(3)-Gd(3)-0(13)  126.5(2)  0(5)-Gd(l)-N(2)  142.4(2)  0(3)-Gd(3)-N(5)  72.0(2)  0(5)-Gd(l)-N(3)  84.0(2)  0(3)-Gd(3)-N(6)  117.7(2)  0(5)-Gd(l)-N(4)  90.9(2)  0(3)-Gd(3)-N(7)  74.6(2)  0(7)-Gd(l)-0(8)  52.1(2)  0(3)-Gd(3)-N(8)  138.6(2)  0(7)-Gd(l)-N(l)  113.5(2)  0(4)-Gd(3)-0(9)  72.5(2)  0(7)-Gd(l)-N(2)  119.4(2)  0(4)-Gd(3)-0(12)  142.7(2)  0(7)-Gd(l)-N(3)  69.8(2)  0(4)-Gd(3)-0(13)  129.2(2)  0(7)-Gd(l)-N(4)  67.7(2)  0(4)-Gd(3)-N(5)  104.3(2)  0(8)-Gd(l)-N(l)  69.9(2)  0(4)-Gd(3)-N(6)  77.8(2)  0(8)-Gd(l)-N(2)  78.1(2)  0(4)-Gd(3)-N(7)  143.3(2)  0(8)-Gd(l)-N(3)  75.4(2)  0(4)-Gd(3)-N(8)  72.2(2)  0(8)-Gd(l)-N(4)  70.8(2)  0(9)-Gd(3)-0(12)  124.7(2)  N(l)-Gd(l)-N(2)  68.7(2)  0(9)-Gd(3)-0(13)  71.6(2)  N(l)-Gd(l)-N(3)  66.5(2)  0(9)-Gd(3)-N(5)  139.1(2)  N(l)-Gd(l)-N(4)  123.3(2)  0(9)-Gd(3)-N(6)  144.3(2)  N(2)-Gd(l>-N(3)  133.5(2)  0(9)-Gd(3)-N(7)  91.7(2)  N(2)-Gd(l)-N(4)  64.5(2)  0(9)-Gd(3)-N(8)  86.6(2)  N(3)-Gd(l)-N(4)  136.2(2)  0(12)-Gd(3)-0(13)  53.1(2)  0(l)-Gd(2)-0(2)  67.2(2)  0(12)-Gd(3)-N(5)  83.2(2)  0(l)-Gd(2)-0(3)  81.4(2)  0(12)-Gd(3)-N(6)  71.5(2)  0(l)-Gd(2)-0(4)  99.4(2)  0(12)-Gd(3)-N(7)  73.5(2)  0(l)-Gd(2)-0(6)  78.8(2)  0(12)-Gd(3)-N(8)  76.0(2)  0(l)-Gd(2)-0(9)  144.7(2)  0(13)-Gd(3)-N(5)  126.3(2)  O(l)-Gd(2)-O(10)  126.7(2)  0(13)-Gd(3)-N(6)  115.5(2)  0(1)-Gd(2)-0(11)  148.0(2)  0(13)-Gd(3)-N(7)  71.9(2)  - 75 -  References on p.  Chapter 3  Table 3.9. Continued. 0(2)-Gd(2)-0(3)  113.7(2)  0(13)-Gd(3)-N(8)  70.9(2)  0(2)-Gd(2)-0(4)  164.8(2)  N(5)-Gd(3)-N(6)  67.3(2)  0(2)-Gd(2)-0(6)  83.6(2)  N(5)-Gd(3)-N(7)  66.3(2)  0(2)-Gd(2)-0(9)  126.7(2)  N(5)-Gd(3)-N(8)  132.3(2)  O(2)-Gd(2)-O(10)  76.5(2)  N(6)-Gd(3)-N(7)  123.9(2)  0(2)-Gd(2)-0(ll)  99.7(2)  N(6)-Gd(3)-N(8)  65.5(2)  0(3)-Gd(2)-0(4)  69.3(2)  N(7)-Gd(3)-N(8)  141.3(2)  Gd(l)-0(1)-Gd(2)  111.9(2)  Gd(2)-0(3)-Gd(3)  102.5(2)  Gd(l)-0(2)-Gd(2)  111.3(2)  Gd(2)-0(4)-Gd(3)  101.3(2)  The X-ray crystal structure of [Sm3(Ll) (CH3COO)2(N03)2(CH OH)][N03] (Figure 2  3  3.7) shows the presence of three Sm(III) ions, two LI ligands with all four phenolate _  oxygen atoms forming bridges, one methanol molecule, two bidentate nitrate groups on two Sm(III) metal centers, and two bridging acetate groups in the classical r^m/ip fashion. 2  Sm(l) is nine coordinate with a monocapped square antiprism geometry. One face of the square is composed of 0(1), 0(2), N(l), and N(2), and the second square is composed of N(3), N(4), 0(5) and 0(8), with 0(7) as the capping atom (as shown for Gd(l) in Figure 3.6). Sm(2) is coordinated to seven oxygen atoms. The geometry around this center is best described as a distorted monocapped trigonal prism with 0(6) as the capping atom (Figure 3.7). Sm(3) has a coordination number of nine; its geometry at the metal center can be best described as a monocapped square antiprism. The faces of the squares consist of atoms 0(3), 0(4), N(5), N(6) and N(7), N(8), 0(11), 0(13) with 0(14) capping the latter face (as shown for Gd(3) in Figure 3.6). - 76 -  References on p. 83  Chapter 3  Figure 3.7. ORTEP diagram of the  [Sm (Ll)2(CH3COO)2(N03)2(CH OH)]  +  3  3  [Sm3(Ll) (CH3COO)2(N03)2(CH30H)]N03»CH OH»3 65H 0 2  3  2  and a scheme  cation in of the  coordination geometry around Sm(2), shown with the same numbering as the crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 33% probability level, and some of the phenolate and pyridyl ring atoms have been omitted for clarity. -77-  References on p. 83  Chapter 3  The polyhedral geometries around Sm(l) and Sm(3) are virtually identical to those of Gd(l) and Gd(3), respectively, with a different numbering system of oxygen atoms around Sm(3) due to the replacement of a bidentate nitrate with a bidentate acetate in [Gd (L3) (CH COO)4(CH OH)][C10 ].  The similarities in the X-ray crystal structures of  [Gd (L3)2(CH COO)4(CH30H)] [C10 ]  and [Sm (L 1 )2(CH COO) (N0 ) (CH OH)] [N0 ]  3  2  3  3  3  4  3  4  3  3  2  3 2  3  3  show that reactions using different Ln(III) starting materials, with either the bromo substituted or unsubstituted ligand, and with two to three equivalents of sodium acetate will produce the same [Ln L2(X)„(CH OH)] complex. +  3  3  Table 3.10 summarizes selected bond angles and bond lengths for the cation of trinuclear [Sm (Ll)2(CH COO)2(N0 )2(CH OH)][N0 ]. The average Sm-N bond length is 3  3  3  3  3  2.618 A, similar to that of samarium ten-coordinated with an iminopyridyl hexadentate ligand (Sm-N (avg) 2.63 A).  56  The average phenolate oxygen atom to Sm(III) bond length is  2.385 A, similar to that in its gadolinium congener even though the ionic radius of Sm(III) is slightly larger than that of Gd(III). The angles at the phenolate oxygen bridgeheads are 3  110.79°, 109.64°, 104.08°, 101.55° at 0(1), 0(2), 0(3) and 0(4), respectively. The intraSm(III) distances are 3.910 A (Sm(l)-Sm(2)) and 3.729 A (Sm(2)-Sm(3)), very similar to, if not even smaller than the Gd-Gd distances in [Gd (L3) (CH COO) (CH OH)][C10 ]. In 3  2  3  4  3  4  the trinuclear Sm(III) complex, there is only one type of acetate present, the classical ri^ri^p fashion bridging acetate. The average of Sm-0(bridging acetate) is 2.393 A, 2  consistent with that of [Gd (CH COO)8] \  2 27  2  3  after correcting for the difference in ionic radii  between the two metal ions. The absence of tridentate Cn :^ ^ fashion) acetate is the only 2  3  1  2  difference between the two trinuclear Sm(III) and Gd(III) complexes. This difference may be due to the larger ionic radius of Sm(III), pushing the distance of 0(11) to Sm(2) to be too - 78 -  References on p. 83  Chapter 3  large for a bond to be formed. The Sm-O(nitrate) bond lengths are also consistent with other Sm(III)  complexes containing bidentate nitrate. " 56  58  The bond length of Sm-O(MeOH) is  2.489 A , similar to its Gd congener (vide supra).  Table 3.10. Selected Bond Lengths (A) and Bond Angles (deg) in the Cation of [Sm3(Ll)2(CH3COO)2(N03)2(CH30H)][N03]'CH OH'3.65H20. 3  Sm(l)-Sm(2)  3.910(14)  Sm(2)-Sm(3)  3.726(12)  Sm(l)-0(1)  2.385(4)  Sm(2)-0(6)  2.337(4)  Sm(l)-0(2)  2.406(3)  Sm(2)-O(10)  2.469(4)  Sm(l)-0(5)  2.361(4)  Sm(2)-0(12)  2.489(4)  Sm(l)-0(7)  2.580(4)  Sm(3)-0(3)  2.353(4)  Sm(l)-0(8)  2.569(4)  Sm(3)-0(4)  2.411(4)  Sm(l)-N(l)  2.697(4)  Sm(3)-0(11)  2.404(4)  Sm(l)-N(2)  2.626(4)  Sm(3)-0(13)  2.525(4)  Sm(l)-N(3)  2.585(5)  Sm(3)-0(14)  2.543(4)  Sm(l)-N(4)  2.540(5)  Sm(3)-N(5)  2.715(4)  Sm(2)-0(1)  2.365(4)  Sm(3)-N(6)  2.609(4)  Sm(2)-0(2)  2.377(4)  Sm(3)-N(7)  2.616(4)  Sm(2)-0(3)  2.377(4)  Sm(3)-N(8)  2.552(4)  Sm(2)-0(4)  2.403(4)  0(l)-Sm(l)-0(2)  65.60(12)  0(3)-Sm(2)-0(4)  69.14(11)  0(l)-Sm(l)-0(5)  78.75(13)  0(3)-Sm(2)-0(6)  139.48(13)  0(l)-Sm(l)-0(7)  137.51(12)  O(3)-Sm(2)-O(10)  79.29(13)  0(l)-Sm(l)-0(8)  148.89(13)  0(3)-Sm(2)-0(12)  140.24(13)  0(1)-Sm(l)-N(l)  73.69(13)  0(4)-Sm(2)-0(6)  83.48(13)  0(1)-Sm(l)-N(2)  111.07(13)  O(4)-Sm(2)-O(10)  114.14(13)  0(1)-Sm(l)-N(3)  83.69(14)  0(4)-Sm(2)-0(12)  92.54(13)  -79-  References on p. 83  Chapter 3  Table 3.10. Continued 0(1)-Sm( 1)-N(4)  136.92(13)  O(6)-Sm(2)-O(10)  140.64(14)  0(2)-Sm( 1HX5)  86.42(12)  0(6)-Sm(2)-0(12)  67.14(13)  0(2)-Sm( 1HX7)  131.59(12)  O(10)-Sm(2)-O(12)  76.77(13)  0(2)-Sm( 1HX8)  138.25(12)  0(3)-Sm(3)-0(4)  69.38(11)  0(2)-Sm( l)-N(l)  108.61(13)  0(3)-Sm(3)-0(ll)  70.86(12)  0(2)-Sm( 1)-N(2)  75.71(13)  0(3)-Sm(3)-0(13)  146.48(12)  0(2)-Sm( 1)-N(3)  148.74(14)  0(3)-Sm(3)-0(14)  126.80(12)  0(2)-Sm( 1)-N(4) .  72.57(13)  0(3)-Sm(3)-N(5)  74.03(13)  0(5)-Sm( l)-0(7)  66.32(13)  0(3)-Sm(3)-N(6)  119.08(13)  0(5)-Sm( l)-0(8)  115.98(13)  0(3)-Sm(3)-N(7)  78.73(13)  0(5)-Sm( l)-N(l)  138.75(14)  0(3)-Sm(3)-N(8)  139.96(14)  0(5)-Sm( 1)-N(2)  152.73(14)  0(4)-Sm(3)-0(ll)  72.96(13)  0(5)-Sm( 1)-N(3)  81.78(14)  0(4)-Sm(3)-0(13)  141.32(11)  0(5)-Sm( 1)-N(4)  89.11(14)  0(4)-Sm(3)-0(14)  130.99(12)  0(7)-Sm( l)-0(8)  49.84(12)  0(4)-Sm(3)-N(5)  105.29(13)  0(7)-Sm( l)-N(l)  118.36(13)  0(4)-Sm(3)-N(6)  76.57(14)  0(7)-Sm( 1)-N(2)  111.04(14)  0(4)-Sm(3)-N(7)  148.10(13)  0(7)-Sm( 1)-N(3)  68.55(14)  0(4)-Sm(3)-N(8)  74.24(13)  0(7)-Sm( 1)-N(4)  68.03(13)  0(11)-Sm(3)-0(13)  122.89(13)  0(8)-Sm( l)-N(l)  78.29(14)  0(11)-Sm(3)-0(14)  71.95(14)  0(8)-Sm( 1)-N(2)  69.12(13)  0(11)-Sm(3)-N(5)  142.95(13)  0(8)-Sm( 1)-N(3)  72.41(15)  0(11)-Sm(3)-N(6)  141.36(14)  0(8)-Sm( 1)-N(4)  73.08(14)  0(11)-Sm(3)-N(7)  96.78(14)  N(l)-Sm( 1)-N(2)  67.71(14)  0(11)-Sm(3)-N(8)  83.13(14)  N(l)-Sm( 1)-N(3)  65.37(14)  0(13)-Sm(3)-0(14)  51.12(12)  N(l)-Sm( 1)-N(4)  131.75(14)  0(13)-Sm(3)-N(5)  82.31(13)  N(2)-Sm( 1)-N(3)  123.66(14)  0(13)-Sm(3)-N(6)  71.25(13)  N(2)-Sm( 1)-N(4)  66.11(14)  0(13)-Sm(3)-N(7)  69.73(13)  N(3)-Sm( 1)-N(4)  135.63(15)  0(13)-Sm(3)-N(8)  73.42(14)  0(1)-Sm(2)-0(2)  66.37(12)  0(14)-Sm(3)-N(5)  123.31(13)  - 80 -  References on p. 83  Chapter 3  Table 3.10. Continued 0(l)-Sm(2)-0(3)  80.07(12)  0(14)-Sm(3)-N(6)  113.81(14)  0(l)-Sm(2)-0(4)  101.75(12)  0(14)-Sm(3)-N(7)  69.39(13)  0(l)-Sm(2)-0(6)  76.90(12)  0(14)-Sm(3)-N(8)  68.58(13)  O(l)-Sm(2)-O(10)  128.08(12)  N(5)-Sm(3)-N(6)  68.30(13)  0(1)-Sm(2)-0(12)  139.40(13)  N(5)-Sm(3)-N(7)  64.66(13)  0(2)-Sm(2)-0(3)  113.15(12)  N(5)-Sm(3)-N(8)  132.98(14)  0(2)-Sm(2)-0(4)  166.43(12)  N(6)-Sm(3)-N(7)  121.40(14)  0(2)-Sm(2)-0(6)  87.25(13)  N(6)-Sm(3)-N(8)  65.98(14)  O(2)-Sm(2)-O(10)  79.22(13)  N(7)-Sm(3)-N(8)  135.69(14)  0(2)-Sm(2)-0(12)  92.96(13)  Sm(l)-0(1)-Sm(2)  110.79(15)  Sm(2)-0(3)-Sm(3)  104.08(12)  Sm(l)-0(2)-Sm(2)  109.64(14)  Sm(2)-0(4>-Sm(3)  101.55(11)  9  9  The hexadentate ligands (LI "-L3 ") reported herein are unique in their ability to accommodate different sizes of Ln(III) ions in the presence of small potentially bridging ligands, such as nitrate and acetate. Myriad types of coordination modes were discovered: the commonly known seven-coordination monocapped trigonal prism, eight-coordination dodecahedron, square antiprism and bicapped trigonal prism, nine-coordination monocapped square antiprism, tricapped trigonal prism and a rare eight-coordinate cubic geometry. The formation of binuclear complexes of the larger Ln(III) ions with L " was not unexpected since ligands with phenolate oxygen atoms have been known to form bridges between two metal ions. > > These oxygen atoms are drawn to bridge as a requirement of 21  23  51  the higher coordination number for Ln(III) ions. A designed mismatch between Ln(III) coordination numbers and ligand denticity can be used to create new multimetallic motifs. It - 81 -  References on p. 83  Chapter 3  was not expected that the use of acetate as a base would produce different complexes (trinuclear) which contain bridging phenolate oxygen atoms as well as bridging acetates. Ln2[N4C>3]2 complexes were synthesized with either sodium hydroxide or sodium acetate as 51  a base. As well, Caravan et al. have reported the complexation of a ligand which contains 19  two pyridyl and two acetate pendant arms on an ethylenediamine backbone (bis-(2pyridylmethyl)ethylenediamine-N.N'-diacetic acid (Hbped)) with Ln(III) ions. The use of 2  sodium acetate base in the reactions of Ln(III) with either Liu's aminephenolate  [N4O3]  5 1  or  Caravan's LLbped did not produce any trinuclear complexes. Since no trinuclear Ln(III) 19  complexes are formed with aminophenolate '  43 51  and aminopyridyl carboxylate ligands 19  even in the presence of acetate, the formation (reported in this chapter) of trinuclear complexes with aminopyridyl phenolate ligands suggests the stability of this system. This stability is also evinced by the ease of conversion from either mononuclear or dinuclear to trinuclear complexes as long as acetate anion is present (Scheme 3.2 on p. 51) and by the presence of high molecular weight trinuclear complex parent peaks of trinuclear complexes in the mass spectra. *  •  2  2  2  In conclusion, three types of Ln(III) complexes with LI ', L2 " or L3 " have been synthesized and characterized. The formation of each type of complex depends on the size of Ln(III) ions and on the base used in the reaction (NaOH produces mononuclear and dinuclear complexes while sodium  acetate produces trinuclear complexes).  The X-ray crystal  structures of the dinuclear and trinuclear complexes show the presence of bridging phenolate oxygen atoms in both, and bridging acetate groups in the latter. The conversion from mononuclear or dinuclear to trinuclear complexes can be easily performed by adding at least two equivalents of sodium acetate and one equivalent of Ln(III) salt. - 82 -  References on p. 83  Chapter 3  3.4. References 1)  Lanthanide Probes in Life, Chemical and Earth Sciences;  Biinzli, J.-C. G.; Choppin, G.  R., Eds.; Elsevier: Amsterdam, 1989. 2)  Martin, R. B. in Calcium in Biology; Spiro, T. G., Ed.; Wiley: New York, 1983, p 237.  3)  Shannon, R. D. Acta Crystallogr. Sect. A  4)  Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry; 4th. Ed.; John Wiley &  1976, 32, 751.  Sons: New York, 1980. 5)  Karraker, D. G. J. Chem. Educ. 1970, 47, 424.  6)  Evans, C. H. Biochemistry of Lanthanides; Plenum: New York, 1990, p. 47.  7)  Spedding, F. H. In Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edn.; Grayson, M., Eckroth, D., Eds.; Wiley: New York, 1982; Vol. 19, p. 833.  8)  Kahn, O. Struct. Bonding (Berlin) 1987, 68, 89.  9)  Kahn, O. Molecular Magnetism; VCH: New York, 1993.  10) Kahn, O. Adv. Inorg. Chem. 1995, 43, 179. 11) Jurisson, S.; Berning, D.; Jia, W.; Ma, D. Chem. Rev. 1993, 93, 1137. 12) Order, S. E.; Klein, J. L.; Leicher, P. K.; Frinke, J.; Collo, C; Carlo, D. J. Int. J. Radiat. Oncol. Biol. Phys. 1986,12,  277.  13) Cox, J. P. L.; Jakowski, K. J.; Kataky, R; Beely, R. A.; Boyce, B. A.; Eaton, M. A. W.; Miller, K.; Millican, A. T.; Harrison, S.; Walker, C ; Parker, D. J. Chem. Soc. Chem. Comm. 1 9 8 9 , 797.  14) Norman, T. J.; Parker, D.; Royle, L.; Harrison, A.; Antoniw, P.; King, D. J. J. Chem. Soc. Chem. Comm. 1995, 1877.  15) Parker, D. Chem. Br. 1994, 30, 818.  -83-  Chapter 3  Lauffer, R. B. Chem. Rev. 1987, 87, 901. The September 1999 issue of Chem. Rev. 99, is dedicated to medicinal inorganic chemistry topics. Caravan, P.; Lowe, M. P.; Read, P. W.; Rettig, S. J.; Yang, L.-W.; Orvig, C. J. Alloys Compd. 1997, 249, 49 and references therein.  Caravan, P.; Mehrkhodavandi, P.; Orvig, C. Inorg. Chem. 1997, 36, 1316. Lowe, M. P.; Caravan, P.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1998, 37, 1637. Guerriero, P.; Tamburini, S.; Vigato, P. A. Coord. Chem. Rev. 1995,139, 17. Aguiari, A.; Brianese, N.; Tamburini, S.; Vigato, P. A. Inorg. Chim. Acta 1995, 233. Howell, R. C ; Spence, K. V. N.; Kahwa, I. A.; White, A. J. P.; Williams, D. J. J. Chem. Soc, Dalton Trans. 1996,  961.  Chen, L.; Breeze, S. R; Rousseau, R. J.; Wang, S.; Thompson, L. K. Inorg. Chem. 1995, 34, 454.  Wang, S.; Pang, Z.; Smith, K. D. L.; Hua, Y.-S.; Deslippe, C ; Wagner, M. J. Inorg. Chem. 1995, 34, 908.  Daitch, C. E.; Hampton, P. D.; Duesler, E. N.; Alam, T. M. J. Am. Chem. Soc. 1996, 118, 7769. Smith, P. H.; Ryan, R. R. Acta Crystallogr., Sect. C1992, 48,2127. Ouchi, A.; Suzuki, Y.; Ohki, Y.; Koizumi, Y. Coord. Chem. Rev. 1988, 92, 29. Chang, C. A.; Francesconi, L. C ; Malley, M. F.; Kumar, K.; Gougoutas, J. Z.; Tweedle, M. F. Inorg. Chem. 1993, 32, 3501. 30)  Hedinger, R.; Ghisletta, M.; Hegetschweiler, K.; Toth, E.; Merbach, A. E.; Sessoli, R.; Gatteschi, D.; Gramlich, V. Inorg. Chem. 1998, 37, 6698.  -84-  Chapter 3  31) Blake, A. J.; Doble, D. M. J.; Li, W.-S.; Schroder, M. J. Chem. Soc, Dalton Trans. 1997, 3655. 32) Read, P. W.; Xu, Z.; Hibbs, D. E.; Hursthouse, M. B.; Abdul Malik, K. M.; Patrick, B. O.; Rettig, S. J.; Seid, M.; Summers, D. A.; Young, V. G.; Thompson, R. C ; Orvig, C. Manuscript submitted for publication. 33)  Diehl, D.; Hach, C. C. Inorg. Synth. 1950, 3, 196.  34) Wong, E.; Liu, S.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1995, 34, 3057. 35) Hart, F. A.; Laming, F. P. J. Inorg. Nucl. Chem. 1965, 27, 1605. 36) Mehrotra, R. C ; Batwara, J. M. Inorg. Chem. 1970, 9, 2505. 37) Deacon, G. B.; Phillips, R. J. Coord. Chem. Rev. 1980, 33, 227. 38) Liu, S.; Gelmini, L.; Rettig, S. J.; Thompson, R. C ; Orvig, C. J. Am. Chem. Soc. 1992, 114, 6081.  39) Kepert, D. L. J. Chem. Soc. 1965, 4736. 40) Blight, D. G.; Kepert, D. L. Theor. Chim. Acta 1968,11, 51. 41) Blight, D. G.; Kepert, D. L. Inorg. Chem. 1972,11, 1556. 42) Baraniak, E.; Bruce, R. S. L.; Freeman, H. C ; Hair, N. J.; James, J. Inorg, Chem. 1976, 15, 2226. 43) Yang, L.-W.; Liu, S.; Wong, E.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1995, 34, 2164.  44) Sherry, E. G. J. Inorg. Nucl. Chem. 1978, 40,257. 45) Smith, G. D.; Caughlan, C. N.; Mahzar-Ul-Haque; Hart, F. A. Inorg. Chem. 1973, 12, 2654. 46) Burdett, J. K.; Hoffmann, R; Fay, R. C. Inorg. Chem. 1978,17, 2553. 47) Muetterties, E. L.; Wright, C. H. Q. Rev., Chem. Soc. 1967, 21, 109.  -85-  Chapter 3  48) Lippard, S. J. Prog. Inorg. Chem. 1967, 8,109. 49) Sinha, S. P. Struct. Bonding 1976, 25, 69. 50) Al-Karaghouli, A. R.; Day, R. O.; Wood, J. S. Inorg. Chem. 1978,17, 3702. 51) Liu, S.; Yang, L.-W.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1993, 32, 2773. 52) Kahwa, I. A.; Fronczek, F. R; Selbin, J. Inorg. Chim. Acta 1987,126, 227. 53) Kahwa, I. A.; Selbin, J.; O'Connor, C. J.; Foise, J. W.; McPherson, G. L. Inorg. Chim. Acta 1988,148, 265.  54) Drew, H. G. B. Coord. Chem. Rev. 1977,24,179. 55) Bligh, S. W. A.; Choi, N.; Cummins, W. J.; Evagorou, E. G.; Kelly, J. D.; McPartlin, M. J. Chem. Soc. Dalton Trans. 1993, 3829. 56) Abid, K. K.; Fenton, D. E.; Casellato, U.; Vigato, P. A.; Graziani, R. J. Chem. Soc. Dalton Trans. 1984, 351.  57) Burns, J. H. Inorg. Chem. 1979,18, 3044. 58) Tomat, G.; Valle, G.; Cassol, A.; Di Bernardo, P. Inorg. Chim. Acta 1983, 76, LI3.  -86-  CHAPTER 4  Iron(III) C o m p l e x with a Hexadentate Aminopyridylphenolate L i g a n d  4.1. Introduction  Iron(III) is an example of metal ions that are present in metalloproteins and metalloenzymes, such as transferrin, lactoferrin, catecholate dioxygenases and purple acid phosphatases. Transferrin is an iron transport protein that binds tightly to Fe(III) ions. '  1 2  Lactoferrin belongs to the same family, and is present in high concentration in human milk. ' Catecholate dioxygenases ' catalyze general reactions below: 3 4  5 6  Scheme 4.1.  Purple acid phosphatases catalyze the hydrolysis of activated phosphoric acid esters. " All 7  10  the above belong to a subclass of iron-tyrosinate proteins in which the interactions of iron 11  with one or more phenolate moieties of the amino acid tyrosine play essential roles in the functions and the stabilization of the geometries of the active sites.  -87-  References on p. 100  Chapter 4  Model compounds have been synthesized to mimic the environment in the active sites of iron-tyrosinate proteins. ' ' ' '  1 2 6 9 12-15  Most of the model small molecules studied contain  ligands with nitrogen (aliphatic and/or aromatic) and oxygen (phenolate and/or carboxylate) donor atoms. Pyridyl (py) groups have been used in metalloprotein modeling studies as a mimic of the histidine amino acid in the active sites; * moreover, polypyridyl ligands also 12  14  have a potential application as heavy metal chelators in biochemical studies. N,N,N',N'Tetrakis(2-pyridylmethyl)ethylenediamine (tpen) was used in studies of the effect of ironchelating agents on the toxicity of doxorubicin to MCF-7 human breast cancer cells.  In a  recent in vitro study, Fe -tpen was found to exhibit a hepatoprotective effect on  CCI4-  16  n  induced liver inj ury in rats.  17  In this chapter, the coordination chemistry of Fe(III) with a potentially hexadentate pro-ligand H2LI  (N,N'-bis(2-hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine,  Fbbbpen) will be discussed. This study is an expansion of our research on homomultinuclear Ln(III) complexes (see Chapter 3) to heteromultinuclear Ln(III)/M complexes (M n+  n+  = 3d-  metal ions) using this ligand system, and an extension to our study in the co-aggregation of d- and f-metal ions with aminophenolates. The reactions of Ga(III) and In(III) with H2LI18  H2L3 pro-ligands were previously investigated in our group, resulting in the formation of 19  monocationic [M(L)] complexes (M = Ga, In). Model compound studies of metalloenzym.es +  incorporating manganese and vanadium 20  21-24  with H2LI have also been reported.  Z = H,H bbpen(H Ll) = CI, H Clbbpen (H L2) = Br, H Brbbpen (H L3) 2  2  2  2  -88-  2  2  References on p. 100  Chapter 4  4.2. Experimental  Materials.  Hydrated  iron(III)  nitrate,  and  tetra-n-butylammonium  hexafluorophosphate [(TBA)PFe] were obtained from Aldrich and used without further purification.  All other chemicals were obtained from Aldrich or Alfa or synthesized  according to previously published methods as described in section 3.2. Instrumentation. In addition to the instrumentation outlined in section 3.2, UV/vis spectra (with an uncertainty of ± 2 nm) were recorded on a Shimadzu UV-2100 spectrophotometer in acetonitrile. Electrochemical measurements were conducted in the Dr. M. O. Wolfs laboratory on a Pine AFCBP1 bipotentiostat using a Pt disc working electrode, Pt coil wire counter electrode, and Ag wire reference electrode. Cyclic voltammetry experiments were performed at room temperature in C H 3 C N solutions containing 0.25 M [(TBA)PF6] as supporting electrolyte. Decamethylferrocene was used as an internal standard (E1/2 = -0.12 V vs SCE (Standard Calomel Electrode)), and the E1/2 value is reported referenced against SCE. Synthesis of metal complexes. [Fe(Ll)]N0 »CH OH. To a mixture of H L1 (89 3  3  2  mg, 0.19 mmol) and NaOAc (sodium acetate) (34 mg, 0.41 mmol) in 5 mL methanol, solid Fe(N03)3.9H 0 (80 mg, 0.20 mmol) was added. Upon this addition, the solution turned 2  purple immediately, and the solution was stirred for 30 min at room temperature. Suitable crystals for X-ray structural analysis were obtained by slow evaporation of the solvent at room temperature. The resulting purple solid was removed by filtration yielding 35 mg (29%). Anal. Calcd. (found) for [Fe(Ll)]N0 'CH OH 3  3  (C29H 2FeN 0 ): 3  5  6  C, 57.82 (58.04);  H, 5.35 (5.11); N, 11.62 (11.65). Mass spectrum (LSIMS): m/z = 508 ([Fe(Ll)] ), 402 +  ([Fe(C2iH22N40)] ),296([Fe(C Hi N4)] ). IR (cm' , KBr disk): 1605(m), 1594(m), 1476(s), +  +  14  1  6  -89-  References on p. 100  Chapter 4  1453(s) (V  C  1289(s), 1270(s) (5 . ); 1382(s) (free v -)- UV-vis (in CH CN): X  =N =C);  C 0  JC  N03  (e, M" cm"): 575 nm (5400), 323 (8900), 275 (13500). E 1  3  max  = - 0.47 V (± 0.02 V) vs SCE.  1  m  [Fe(Ll)]PF . H bbpen (140 mg, 0.31 mmol) and NaOAc (56 mg, 0.68 mmol) were 6  2  dissolved in a solution of warm methanol (5 mL). To this mixture, Fe(N03)3.9H20 (120 mg, 0.30 mmol) was added, and stirring was continued at room temperature for 15 min. NaPF6 (76 mg, 0.45 mmol) was then added, and the solution was stirred for another 30 min. The resulting purple solid was removed by filtration yielding 125 mg (63%). Anal. Calcd. (found) for [Fe(Ll)]PF (C H F FeN 0 P): C, 51.47 (51.08); H, 4.32 (4.22); N, 8.58 (8.45). 6  Mass  spectrum  28  28  6  (LSIMS):  4  m/z  2  =  508  ([Fe(Ll)] ), +  402  ([Fe(C iH 2N 0)] ), 2  2  4  +  296([Fe(Ci Hi N )] ). TJKcm", KBr disk): 1605(m), 1594(m), 1478(s), 1451(s) (v = , c=c); +  4  6  1  4  c  N  1291(s), 1270(s) (8c-o); 841(s) (free vpp-). The solid state magnetic moment was 5.91 ± 6  0.10 BM. X-ray Crystallographic Analyses. The crystal structure was determined by the late Dr. Steven J. Rettig of the UBC structural chemistry laboratory. An ORTEP drawing of the [Fe(Ll)] cation in [Fe(Ll)]N03 CH OH is presented in Figure 4.1. Selected bond lengths +  #  3  and bond angles are listed in Table 4.1, selected crystallographic data and the complete bond lengths and angles are presented in Table A13 and A14 (Appendix), respectively.  4.3. Results and Discussion A deep purple coloured monocationic [Fe(Ll)] complex was prepared from reactions +  of hydrated iron(III) nitrate with one equivalent of H L1 and two equivalents of sodium 2  acetate in methanol. Both the nitrate and hexafluorophosphate salts of this complex were prepared and both are soluble in methanol, acetonitrile and acetone. They were characterized - 90 -  References on p. 100  Chapter 4  by spectroscopic methods (IR, LSIMS, UV/vis), elemental analyses, magnetic and electrochemical techniques, and the nitrate salt by X-ray crystallography. The IR spectra of the monocationic complex in each salt show medium bands around 1600 cm' and strong bands between 1480-1450 cm" corresponding to C=N (py) and C=C 1  1  stretching vibrations of the aromatic rings. These are consistent with the reported values for Ga(III) and In(III) complexes.  19  The deformation bands of the phenolate C-0 group appear  around 1290-1279 cm", similar to those found in the Ln(III) complexes (see Chapter 3). The 1  free (uncoordinated) anionic NO3" and PF6" have stretching vibrations at 1382 and 860 cm", 1  respectively. The LSI-mass spectra show the presence of [Fe(Ll)] parent peak, as well +  [Fe(C2iH22N40)] and [Fe(Ci4Hi6N4)] fragments, consistent with the loss of one and two +  +  phenolate pendant arms, respectively, from the parent ion. This type of fragmentation is also observed in the Ln(III) (Chapter 3) and Re(V) (Chapter 5) complexes. Crystals of [Fe(Ll)]N03 CH30H suitable for crystal analysis were grown from slow #  evaporation of a methanol solution at room temperature. An ORTEP drawing of the cation in [Fe(Ll)]N03»CH30H is shown in Figure 4.1. The structure shows that hexadentate LI " is bound to the central Fe(III) ion via two amine nitrogen atoms (ethylenediamine backbone), two pyridyl nitrogen atoms and two phenolate oxygen atoms, resulting in a distorted octahedral geometry. Each half of the ligand forms a /ac-N^O arrangement: NI, N3, Ol forms one face of the octahedron, while N2, N4 and 02 forms the other face. The two amine nitrogen atoms and the two phenolic oxygen atoms are each cis, and they form an equatorial plane, relative to which the two pyridyl nitrogen atoms are trans in axial positions. This structure is essentially identical to the Mn(III), V(III), Ga(III) and In(III) analogues. 20  -91 -  21  19  References on p. 100  Chapter 4  The structure of the Ru(III) complex, however, showed two amine nitrogen, two pyridyl nitrogen and two phenolate oxygen atoms all as cis pairs. The cis configuration of the two 25  phenolate oxygen atoms found herein has the potential to form bridges to another metal ion, such as Ln(III) in a heteromultinuclear complex.  Figure 4.1. ORTEP drawing of the [Fe(Ll)] cation in [Fe(Ll)]N0 -CH OH showing the +  3  3  crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 33% probability level.  -92-  References on p. 100  Chapter 4  Table 4.1. Selected Bond Lengths (A) and Bond Angles (deg) in the cation of [Fe(Ll)]N0 -CH OH. 3  Fe(l)-0(1)  1.8610(14)  N(2)-C(16)  1.485(3)  Fe(l)-0(2)  1.8855(15)  N(2)-C(22)  1.487(3)  Fe(l)-N(l)  2.234(2)  N(3)-C(4)  1.339(3)  Fe(l)-N(2)  2.228(2)  N(4)-C(17)  1.352(3)  Fe(l)-N(3)  2.135(2)  C(l)-C(2)  1.511(3)  Fe(l)-N(4)  2.135(2)  C(3)-C(4)  1.500(3)  0(1)-C(11)  1.336(3)  C(9)-C(10)  1.505(3)  0(2)-C(24)  1.338(3)  C(10)-C(ll)  1.415(3)  N(l)-C(l)  1.490(3)  C(16)-C(17)  1.493(3)  N(l)-C(3)  1.484(3)  C(22)-C(23)  1.502(3)  N(l)-C(9)  1.496(3)  C(23)-C(24)  1.422(3)  N(2)-C(2)  1.495(3)  0(l)-Fe(lK)(2)  103.64(6)  Fe(l)-N(l>-C(l)  107.04(13)  0(1)-Fe(l)-N(l)  88.91(6)  Fe(l)-N(l)-C(3)  111.51(14)  0(1)-Fe(l)-N(2)  165.52(7)  Fe(l)-N(l)-C(9)  109.33(12)  0(1)-Fe(l)-N(3)  93.80(7)  C(l)-N(l)-C(3)  110.2(2)  0(1)-Fe(l)-N(4)  93.21(7)  C(l)-N(l)-C(9)  108.7(2)  0(2)-Fe(l)-N(l)  164.93(7)  C(3)-N(1H:(9)  110.0(2)  0(2)-Fe(l)-N(2)  88.77(7)  Fe(l)-N(2)-C(2)  106.65(13)  0(2)-Fe(l)-N(3)  93.37(7)  Fe(l)-N(2)-C(16)  110.50(13)  0(2)-Fe(l)-N(4)  96.88(7)  Fe(l)-N(2)-C(22)  108.94)13)  N(l)-Fe(l)-N(2)  80.04(7)  C(2)-N(2)-C(16)  110.7(2)  N(l)-Fe(l)-N(3)  77.28(7)  C(2)-N(2)-C(22)  109.2(2)  N(l)-Fe(l)-N(4)  90.59(7)  C(16)-N(2)-C(22)  110.7(2)  N(2)-Fe(l)-N(3)  92.85(7)  Fe(l)-N(3)-C(4)  118.2(2)  N(2)-Fe(l)-N(4)  77.71(7)  Fe(l>-N(3)-C(8)  122.6(2)  N(3)-Fe(l)-N(4)  165.86(7)  Fe(l)-N(4)-C(17)  118.0(7)  Fe(l)-0(1>-C(ll)  134.70(14)  Fe(l)-N(4)-C(21)  123.4(2)  Fe(l)-0(2)-C(24)  133.48(14)  . 93 -  3  References on p. 100  Chapter 4  Selected bond lengths and bond angles are listed in Table 4.1. The Fe-0 bond lengths have an average of 1.873 A, similar to those in bis(methanol)bis[2-(5-methylpyrazol3-yl)phenolato]iron(III) nitrate (1.888 A), and in a trigonal bipyramidal iron(III) complex 26  with a tetradentate tripodal amine phenolate (N0  3  donor set) and monodentate  methylimidazole ligand ([Fe{N(CH -0-C H 0) }(l-Meim)]) (1.876 A ) 2  6  4  3  27  The average Fe-  N(amine) bond length of 2.231 A and Fe-N(py) bond length of 2.135 A are comparable to those found in the dinuclear iron complexes with H bhpp (l,3-bis[(2-hydroxybenzyl)(23  pyridylmethyl)amino]-2-propanol)  and  Hbhpmp 3  (2,6-bis[((2-hydroxybenzyl)(2-  pyridylmethyl)aminomethyl] -4-methylphenol).  12  The three trans angles OT-Fe-N2, 02-Fe-Nl, and N3-Fe-N4 are 165.52(7)°, 164.93(7)° and 165.86(7)°, respectively, a deviation of-15° from 180°. The cis Nl-Fe-N2 (amines) angle is 80.04(7)°, and the cis N(amine)-Fe-N(py) angles (Nl-Fe-N3 and N2-FeN4) within the two five-membered chelate rings are 77.28(7)° and 77.71(7)°, respectively. All other cis angles in the complex are close to 90°, except the cis OT-Fe-02 angle of 103.64(6)°, a deviation of-14° from 90°. This deviation is similar to that found in V(III)  21  and In(III) congeners, but was not observed in the Ga(III), and Mn(III) analogues, even 19  19  20  though the ionic radius of high spin Fe(III) (0.643 A) is similar to those of Ga(III) (0.62 A),  -94-  References on p. 100  Chapter 4  V(III) (0.640 A ) and Mn(III) (0.645 A), but significantly smaller than that of In(III) (0.800 A)28 The magnetic moment of [Fe(Ll)]PF6 at room temperature was measured to be 5.91 BM. This value is in excellent agreement with the spin-only value of 5.92 B M for a high spin Fe(III) ion. The electronic spectrum of [Fe(Ll)]NC»3 in C H 3 C N is presented in Figure 4.2. It consists of three maxima (l  max  ) at 575 nm (s = 5400 M" cm' ), 323 (8900), and 275 (13500). 1  1  The electronic spectrum of H2LI does not show any absorption maxima above 300 nm;  20  thus, the two lower energy bands are assigned as ligand to metal charge transfer bands (LMCT). Due to the intense LMCT bands, spin forbidden d-d transitions in the high spin d Fe(III) ion were not observed in this complex.  400  500 600 wavelength (nm)  700  800  Figure 4.2. UV/visible spectrum of 62 pM [Fe(Ll)]N0 in acetonitrile. 3  -95-  References on p. 100  s  Chapter 4  The 575 nm band is assigned to the charge transfer transition from prc orbital of the phenolate oxygen to the dn* orbital of Fe(III) (see Figure 4.3 on p. 97). '2,26,29,30 This band is similar to that in the dinuclear iron(III) complex with bhpp" and two diphenyl phosphato 3  ligands, A,  = 586.5 (sic) nm (e = 1150 M" cm'VFe); the geometry around each iron(III) 1  max  center was octahedral with a phosphato ligands).  12  N2O4  donor set (two oxygen atoms from two diphenyl  However, the pn —> dn* transition is at a lower energy compared to  that in an iron(III) complex with a tetradentate N,N'-bis(2-hydroxybenzyl)ethylenediamine  (H2bben) and two monodentate imidazole ligands (490 nm). Ainscough et al. suggested 26  26  a structure for the [Fe(bben)(Im)2] with two cis phenolate oxygen atoms and two trans +  imidazole nitrogen atoms, similar to that of [Fe(Ll)] reported herein with the trans pyridyl +  nitrogen atoms replacing those of imidazole in the former. The bathochromic shift of the charge transfer bands of [Fe(Ll)] is consistent with the tighter bonding of the hexadentate +  ligand LI ", which gives a better phenolate-iron overlap, compared to a combination of one 2  tetradentate (N2O2) and two monodentate imidazole ligands. The ligand field strengths of imidazole and pyridyl ligands may also play a role in this red shifted absorption maximum. A relationship between the energy of the phenolate to iron(III) charge transfer transition and the field strength of ligands coordinated to iron(III) center has been observed previously. '  26 31  -96-  References on p. 100  Chapter  4  Another similar complex, that o f iron(III) with the linear N4O2 amine phenolate ligand  26  ^max  507 nm. B y analogy to the structure o f the Ga(III) complex with hexadentate  =  (l,12-bis(2-hydroxyphenyl)-2,5,8,ll-tetraazadodecane, also known as Fl^bad ), has 32  the Fe(III) structure with the same l i g a n d  bad ", 2  32  can be postulated to have a similar distorted  26  octahedral geometry, in which all four adjacent amine nitrogen atoms are cis to one another because o f the steric constraints o f the trien (triethylenetetramine) backbone. I f this were the case, the N4O2 donor atom set o f [Fe(bad)]  +2S  would be similar to that o f [ F e ( L l ) ] ; however, +  the former would have a more sterically constrained structure dictated by the presence o f three five-membered chelate rings instead o f two in the latter complex. The reduced steric strain in [ F e ( L l ) ] should improve the phenolate to iron orbital overlap, thus facilitating the +  charge transfer transition giving a lower energy L M C T band.  drj*  lODq  l  2g  P7t  P7I Metal d-orbitals (assuming octahedral geometry)  0(phenolate)  Figure 4.3. Qualitative energy level diagram showing the effect o f ligand phenolate puorbital interaction with d-orbitals o f i r o n ( I I I ) .  33  -97-  References  on p.  100  Chapter 4  The higher energy LMCT band at 323 nm is associated with the transition from the phenolate pit orbital to iron(III) da* orbital (Figure 4.3). > > > 12  26  29  30  The energy difference  between the two LMCT bands (-13,500 cm") is a measure of lODq for this octahedral 1  complex. This value is similar to that of octahedral [Fe(EDDHA)]" complex (~11000 cm" )  1 29  and [Fe(OH ) ] (13,700 cm" ). 3+  2  1  34  6  HOOC  COOH  EDDHA  The cyclic voltammogram of [Fe(Ll)]NC>3 was recorded in acetonitrile in the range of -0.9 to 0.1 V versus SCE. It exhibits a reversible reduction wave at E1/2 = -0.47 V (AE = P  100 mV). This quasi-reversible one electron redox process is assigned to [Fe (Ll)] + e" <-» ra  +  [Fe (Ll)]. n  -1  1  1  1  1  -0.8  -0.7  -0.6  -0.5  -0.4  1  1  -0.3  -0.2  r -0.1  Voltage (Vvs SCE)  Figure 4.4. Cyclic voltammogram of [Fe(Ll)]N0 in CH CN (0.25 M (TBA)PF ), scan rate 3  3  6  is 100 mVs" . 1  - 98 -  References on p. 100  Chapter 4  In conclusion, monocationic [Fe(Ll)] complexes were synthesized with two +  different counter anions (NCV and PF6).  The magnetic susceptibility measurement  -  confirmed the presence of high spin iron(III). The crystal structure of [Fe(Ll)]N0 showed a 3  distorted octahedral geometry around iron(III) with two cis amine nitrogen atoms, two cis oxygen phenolate atoms and two trans pyridyl nitrogen atoms, an arrangement similar to those in the V(III), Mn(III), Ga(III) and In(III) congeners. 21  20  19  The electronic absorption  spectrum of [Fe(Ll)]NC»3 exhibited two LMCT bands at 575 and 323 nm. The 575 nm band is similar to the model studies of purple acid phosphatases active sites, ; however, it is at a 12  lower energy compared to other iron(III) complexes with small ligands used as model studies of transferrin and lactoferrin active sites. '  The lODq value of octahedral [Fe(Ll)] is  26 29  +  calculated to be approximately 13,500 cm , in good agreement with other iron(III) -1  octahedral complexes. '  29 34  -99-  References on p. 100  Chapter 4  4.4. References  1)  Harris, D. C ; Aisen, P. In Iron Carriers and Iron Proteins; Loehr, T. M., Ed.; VCH: New York, 1989, p. 239.  2)  Aisen, P. In Iron Carriers and Iron Proteins; Loehr, T. M., Ed.; VCH: New York, 1989, p. 353.  3)  Feeney, R. E.; Komatsu, S. S. Struct. Bonding (Berlin) 1966,1, 149.  4)  Hennart, P. F.; Brasseur, D. J.; Delogne-Desnoeck, J. B.; Dramaix, M. M.; Robyn, C. E. Am. J. Clin. Nutr. 1991, 53, 32.  5)  Que, L., Jr. In Iron Carriers and Iron Proteins; Loehr, T. M., Ed.; VCH: New York, 1989, p. 467.  6)  Que, L., Jr.; Ho, R. Y. N. Chem. Rev. 1990, 90, 2607.  7)  Doi, K.; Antanaitis, B. L.; Aisen, P. Struct. Bonding 1988, 70, 1.  8)  Que, L., Jr.; True, A. E. Prog. Inorg. Chem. 1990, 38, 97.  9)  Vincent, J. B.; Olivier-Lilley, G. L.; Averill, B. A. Chem. Rev. 1990, 90, 1447.  10) Than, R; Feldmann, A. A.; Krebs, B. Coord. Chem. Rev. 1999,182, 211. 11)  Que, L., Jr. Coord. Chem. Rev. 1983, 50, 73.  12) Krebs, B.; Schepers, K.; Bremer, B.; Henkel, G.; Althaus, E.; Muller-Warmuth, W.; Griesar, K.; Haase, W. Inorg. Chem. 1994,33,1907. 13) Neves, A.; De Brito, M. A.; Vencato, I.; Drago, V.; Griesar, K.; Haase, W. Inorg. Chem. 1996, 35, 2360.  14) Lambert, E.; Chabut, B.; Chardon-Noblat, S.; Deronzier, A.; Chottard, G.; Bousseksou, A.; Tuchagues, J.-P.; Laugier, J.; Bardet, M.; Latour, J.-M. J. Am. Chem. Soc. 1997, 119, 9424.  -100-  Chapter 4  15) Viswanathan, R.; Palaniandavar, M.; Balasubramanian, T.; Muthiah, T. P. Inorg. Chem. 1998, 37, 2943. 16) Doroshow, J. H. Biochem. Biophys. Res. Commun. 1986,135, 330. 17) Moon, J.-O.; Park, S.,-K.; Nagano, T. Biol. Pharm. Bull. 1998,21, 284. 18) Read, P. W.; Xu, Z.; Hibbs, D. E.; Hursthouse, M. B.; Abdul Malik, K. M.; Patrick, B. O.; Rettig, S. J.; Seid, M.; Summers, D. A.; Young, V. G.; Thompson, R. C ; Orvig, C. Manuscript submitted for publication. 19) Wong, E.; Liu, S.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1995, 34, 3057. 20) Neves, A.; Erthal, S. M. D.; Vencato, I.; Ceccato, A. S.; Mascarenhas, Y. P.; Nascimento, O. R.; Horner, M.; Batista, A. A. Inorg. Chem. 1992, 31, 4749. 21) Neves, A.; Ceccato, A. S.; Erthal, S. M. D.; Vencato, I.; Nuber, B.; Weiss, J. Inorg. Chim. Acta 1991,187, 119.  22) Neves, A.; Ceccato, A. S.; Vencato, I.; Mascarenhas, Y. P.; Erasmus-Buhr, C. J. Chem. Soc, Chem. Commun. 1992, 652.  23) Neves, A.; Ceccato, A. S.; Erasmus-Buhr, C ; Gehring, S.; Haase, W.; Paulus, H.; Nascimento, O. R.; Batista, A. A. J. Chem. Soc, Chem. Commun. 1993, 1782. 24) Neves, A.; Romanowski, S. M. M.; Vencato, I.; Mangrich, A. S. J. Chem. Soc, Dalton Trans. 1998,617.  25) Neves, A.; De Brito, M. A.; Oliva, G.; Nascimento, O. R.; Panepucci, E. H.; Batista, A. A. Polyhedron 1995,14, 1307.  26) Ainscough, E. W.; Brodie, A. M.; Plowman, J. E.; Brown, K. L.; Addison, A. W.; Gainsford, A. R. Inorg. Chem. 1980,19, 3655. 27) Hwang, J.; Govindaswamy, K.; Koch, S. A. Chem. Commun. 1998, 1667.  -101 -  Chapter 4  28)  Shannon, R. D. Acta Crystallogr. Sect. A 1976, 32, 751.  29)  Gaber, B. P.; Miskowski, V.; Spiro, T. G. J. Am. Chem. Soc. 1974,96, 6868.  30)  Wang, S.; Wang, L.; Wang, X.; Luo, Q. Inorg. Chim. Acta 1997,254,11.  31)  Pyrz, J. W.; Roe, L.; Stern, L. J.; Que. L., Jr. J. Am. Chem. Soc. 1985,107, 614.  32)  Wong, E.; Liu, S.; Lugger, T.; Hahn, F. E.; Orvig, C. Inorg. Chem. 1995, 34, 93.  33)  Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry; 4th ed.; John Wiley & Sons: New York, 1980, p. 634.  34)  Gray, H. B.; Schugar, H. J. In Inorganic Biochemistry; Eichhorn, G. I., Ed.; Elsevier: Amsterdam, 1973.  -102-  CHAPTER 5  O x o r h e n i u m ( V ) Complexes with Hexadentate A m i n o p y r i d y l phenolate Ligands  5.1. Introduction The coordination chemistry of rhenium (Re) currently attracts burgeoning interest because of its physical similarities to technetium (Tc), whose radionuclide ( Tc) has the 99m  most widespread application in diagnostic nuclear medicine. " The attractive properties of 1  99m  5  Tc include an ideal y photon energy of 140 keV, a relatively short half-life (6 h), and  convenient production from a generator. Since all isotopes of Tc are radioactive, Re is often used as its congener in coordination chemistry studies. More recently, the radioisotopes Re and Re have been investigated for potential 186  188  use in therapeutic nuclear medicine by means of P-irradiation.> Both isotopes have suitable 4  6  nuclear properties.  Re has a half-life of 90 h with P-emission of 1070 keV, and 5 mm  tissue penetration.  Re has a half-life of 17 h with a stronger P-emission (2100 keV) and  greater tissue penetration (11 mm) (with potential to treat a larger mass tumour). A  Re  radiopharmaceutical which has been proven to be beneficial in clinical trials for the palliation of bone pain is the Re complex of with hydroxyethylidene diphosphonate (HEDP). > 186  4  7  Despite the similarities between Re and Tc, Re complexes are significantly harder to reduce (easier to oxidize) and kinetically more inert than their Tc analogues. This fact can be  - 103 -  References on p. 115  Chapter 5  advantageous in vivo. The ease of oxidation of Re complexes translates into oxidation to [ReCu]" in vivo, which can be easily eliminated through the kidneys. Re and Tc complexes with multidentate N,0 donor sets have been extensively studied with Schiff base  8-13  and amino phenolate ligands. " Rhenium(III, IV and V) mononuclear 14  20  or multinuclear complexes with ligands containing polypyridyl groups have also been reported. " 21  23  In some cases, the reduction of Re(V) to Re(IV) was aided by polypyridyl  ligands or by PPI13 liberated from the starting material.  21  Previously, our group has prepared various Re(V) and Tc(V) complexes with ligands containing, neutral oxygen, anionic oxygen and phosphorus donor atoms. " Recently, 24  29  complexation of Re and Tc with aminopyridylcarboxyl (LLbped) and aminopyridyl (H2pmen) ligands were studied. -  30 31  As an extension to those studies, the complex of  aminopyridylphenolate (LI " and L2") with oxorhenium(V) was investigated, and the results 2  2  are reported in this chapter.  /  Z = H, H bbpen (H L1) = CI, H Clbbpen (H L2) = Br, H Brbbpen (H L3) 2  2  2  2  2  2  \  H pmen 2  - 104  References on p. 115  Chapter 5  5.2. Experimental Materials.  ReOCl3(PPh3)  32 2  and K2[ReCl ] were synthesized as reported in the 33  6  literature. All chemicals were obtained from Aldrich or Alfa or synthesized according to the previously published methods as described in section 3.2. Instrumentation. In addition to the instrumentation outlined in section 3.2, NMR spectra were recorded on a Bruker AC-200E ( H, 'H-'H COSY) spectrometer and are !  reported as 8 in ppm (± 0.02 ppm) from external TMS. In one complex ([ReO(Ll)] [ReCl6]), 2  mass spectra were obtained in both positive and negative modes. Synthesis of Metal Complexes. [ReO(Ll)]PF . H L1 (92.5 mg, 0.2 mmol) was mixed with 50 pL of 8M NaOH (0.4 6  2  mmol) in 5 mL methanol.  This solution was then added to a 5 mL suspension of  ReOCl (PPli3) (167 mg, 0.2 mmol) in methanol. The mixture was refluxed for 1.5 h at the 3  2  completion at which it was a dark brown solution. It was cooled to room temperature, and NaPF6 (35 mg, 0.2 mmol) was added. The mixture was left at room temperature for slow evaporation over a three day period and then filtered; the resulting light red precipitate was collected by filtration from the dark greenish brown filtrate, yield 35 mg (22%). Suitable crystals were grown from CHsCN/methanol for X-ray diffraction studies. Anal. Calcd. (found) for [ReO(Ll)]PF »0.5H O (CzgH^FgNA.sPRe): C, 41.58 (41.53); H, 3.61 (3.43); N, 6  2  6.93 (6.60). Mass spectrum (LSIMS): m/z = 655 ([ReO(Ll)] ), 443 ([ReO(Ci Hi N )] ). IR +  +  4  6  4  (cm , KBr disk): 946 (v =o), 846 (v -). H NMR data are presented in Table 5.2. -1  ]  Re  PF6  [ReO(L2)]PF . A procedure similar to that for the [ReO(Ll)]PF6 synthesis was 6  followed using H L2 (107 mg, 0.2 mmol). 2  The same workup yielded 38 mg of  [ReO(L2)]PF (22%). Anal. Calcd. (found) for [ReO(L2)]PF -H 0 (C H Cl2F N 04PRe): 6  6  -105-  2  28  28  6  4  References on p. 115  Chapter 5  C, 37.93 (38.14); H, 3.18 (3.18); N, 6.32 (6.21). Mass spectrum (LSIMS): m/z = 723 ([ReO(L2)] ), 443 ([ReO(Ci Hi N )] ). IR (cm , KBr disk): 949 (v =o), 846 (v -). 'H +  +  4  6  -1  4  Re  PF6  NMR data are presented in Table 5.2. [ReO(Ll)] [ReCl ]. To a 5 mL methanolic suspension of K [ReCl ] (95.2 mg, 0.2 2  6  2  6  mmol), a mixture of H L1 (93.7 mg, 0.2 mmol) and 8M NaOH (50 pL, 0.4 mmol) in 5 mL 2  methanol was added. The mixture was refluxed for 23 h. After cooling to room temperature, the solution was filtered. The brown product was collected, washed with water and Et 0, 2  and dried in air, yield 38 mg (40%). Anal. Calcd. (found) for [ReO(Ll)] [ReCl ]-3H 0 2  6  2  (C 6H Cl6N 0 Re3): C, 38.16 (38.03); H, 3.55 (3.29); N, 6.36 (6.47); CI, 12.07 (12.37). 5  62  8  9  Mass spectrum (LSIMS): m/z = 655 ([ReO(Ll)] ), 443 ([ReO(C Hi N )] ), 364[ReCl ]". IR +  +  14  6  4  5  (cm", KBr disk): 946 (v =o). *H NMR data are presented in Table 5.2. 1  Re  X-ray Crystallographic Analyses.  The crystal structure was determined at the  University of Minnesota X-ray crystallographic laboratory. An ORTEP drawing of the cation in [ReO(Ll)]PFg is presented in Figure 5.1. Selected bond lengths and bond angles are listed in Table 5.1, while selected crystallographic data, and the complete list of bond lengths and angles are presented in Table A15 and A16 (Appendix), respectively.  5.3. Results and Discussion  Monocationic [Re O(L)] complexes were synthesized from two different starting v  +  materials: Re OCl (PPh ) and K [Re Cl] . The substitution reaction of Re OCl (PPh ) v  lv  3  3  2  2  v  6  3  3  2  with potentially hexadentate deprotonated ligands L " in the presence of PF6~ counter anion in 2  methanol at reflux temperature resulted in [Re O(L)]PF6 complexes. v  The reaction with  K [Re Cl]6 as a starting material involved aerial oxidation of Re(IV) to Re(V) since the IV  2  -106 -  References on p. 115  Chapter 5  reaction was not kept under inert atmosphere. The resulting monocationic complex from this oxidation reaction was similar to those from the substitution reaction on Re(V), except that the counter anion in the former was ReCV . [ReO(Ll)]2[ReCl6] is soluble only in DMSO, 2  while the PF6~ salts of the two other cationic complexes are soluble in acetonitrile and acetone. Since the filtrate from which the dark pink product was isolated had a dark greenish brown colour, the low yields for all complexes may be attributed to a mixture of Re products in the reaction. The separation of other possible species was not attempted. All complexes were characterized by IR, mass spectrometry, elemental analyses, 'H NMR, and in the case of [ReO(Ll)]PF6, by X-ray crystal structure analysis. The infrared stretching vibration  VR =o e  was found around 950 cm", similar to that in oxorhenium 1  complexes with a potentially pentadentate H^apa (N,N'-3-azapentane-l,5-diylbis(3-(liminoethyl)-6-methyl-2H-pyran-2-4-(3H)-dione) (N3O2 donor set) and with a potentially 28  tridentate mpenOH (N-(2-pyridylmethyl)-2-aminoethanol) (N2O donor set).  34  H C  CH  3  3  mpenOH  H apa 3  In the mass spectra of all three complexes, [ReO(L)] parent peaks are observed. +  Another predominant peak present is that of the [ReO(Ci4Hi N )] (ReON ) fragment, which +  6  4  4  is indicative of the loss of two phenolic pendant arms of the ligand. This fragmentation is also detected in the Ln(III) and Fe(III) complexes with the same ligands (vide infra). The  -107-  References on p. 115  Chapter 5  presence of the [ReCle]" counter anion in [ReO(Ll)]2[ReCl6] was confirmed by the negative 2  mode LSIMS, consistent with the elemental analysis. Suitable crystals for X-ray crystallographic analysis were grown from mixture of CH3CN/CH3OH  at room temperature. The ORTEP drawing of the [ReO(Ll)] cation in +  [ReO(Ll)]PF6 is presented in Figure 5.1.  Figure 5.1. ORTEP drawing of the [ReO(Ll)] cation in [ReO(Ll)]PF showing the +  6  crystallographic numbering. Thermal ellipsoids for the non-hydrogen atoms are drawn at the 33% probability level.  -108 -  References on p. 115  Chapter 5  The structure shows the presence of a C2 axis along the Re=0 linkage bisecting the ethylenediamine (en) backbone in [ReO(Ll)] . This C2 axis is also observed in octahedral +  [Fe(Ll)] (Chapter 4) and dodecahedral [Yb(Ll)N0 ] (Chapter 3). +  3  The LI " ligand is 2  coordinated to the Re =0 core in a hexadentate fashion resulting in a seven coordinate v  complex. The geometry around the Re(V) center can be best described as a distorted pentagonal bipyramid with the two phenolate oxygen atoms (01 and 01 A) at the axial positions.  This geometry is very similar to that in the [ReO(bped)] cation in +  [ReO(bped)][Re04](H2bped = bis-(2-pyridylmethyl)ethylenediamine-N.N'-diacetic acid).  31  Table 5.1.  Selected Bond Lengths (A) and Bond Angles (deg) in the cation of  [ReO(Ll)]PF . 6  Re(l)-0(2)  1.689(3)  Re(l)-0(lA)  ReOMXl)  2.002(2)  Re(l)-N(lA)  Re(l)-N(l)  2.363(2)  Re(l)-N(2A)  Re(l)-N(2)  2.257(2)  2.002(2)  a  2.363(2)  a  2.257(2)  a  143.59(6)  0(2)-Re(l)-0(lA)  101.73(6)  0(2)-Re(l)-N(lA)  0(2)-Re(l)-0(l)  101.73(6)  0(lA) -Re(l)-N(lA)  0(lA) -Re(l)-0(l)  156.54(12)  0(l)-Re(l)-N(lA)  0(2)-Re(l)-N(2)  76.40(6)  N(2)-Re(l)-N(lA)  0(1A)-Re(l)-N(2)  87.04(8)  N(2A) -Re(l>-N(lA)  67.38(8)  0(1)-Re(l)-N(2)  98.47(8)  0(2)-Re(l)-N(l)  143.58(6)  76.40(6)  0(lA) -Re(l)-N(l)  80.60(8)  0(lA) -Re(l)-N(2A)  98.47(8)  0(1)-Re(l)-N(l)  80.57(8)  0(l)-Re(l)-N(2A)  87.04(8)  N(2)-Re(l)-N(l)  67.38(8)  152.80(12)  N(2A) -Re(l)-N(l)  139.73(9)  N(lA) -Re(l)-N(l)  72.83(11)  a  a  0(2)-Re(l)-N(2A)  a  a  a  a  N(2)-Re(l)-N(2A)  a  a  a  a  a  a  80.57(8) 80.60(8)  a  139.73(9)  a  a  a  a  a  symmetry operation used to generate equivalent atoms: -x+1, y, -Z+V2  -109-  References on p. 115  Chapter 5  Selected bond lengths and angles are listed in Table 5.1. The Re=02(oxo) bond length is 1.689(3) A, similar to that in [ReO(bped)] (1.719(4) A) , and in other +  31  oxorhenium(V) complexes reported by Botha et al. , by Luo et al. and by Rouschias. 34  35  29  The Re-N(amine) bond length of 2.363(2) A and Re-N(py) bond length of 2.257(2) A are slightly longer than those observed in related complexes. -  31 34  The Re-N(amine) bond length  is longer than of Re-N(py), similar to the monocationic [Fe(Ll)] complex (Chapter 4). The +  Re-0(phenolate) bond length of 2.002(2) A is similar to that reported by Luo et al.  29  As described above, the geometry around the Re(V) center is a distorted pentagonal bipyramid. The largest angle is that of OTA-Re-OT at 156.54(12)° a deviation of -24° from the ideal 180°. The equatorial plane consists of the Re=0 oxygen atom, the two amine nitrogen and the two pyridyl nitrogen atoms with the total angles among them adding together to very close to 360°. This shows that the pentagon formed by those atoms is indeed quite planar. The Nl(amine)-Re-NlA(amine) angle within one five-membered chelate ring is 72.83(11)°, slightly larger than that in eight-coordinate dodecahedral [Yb(Ll)N0 ] 3  (Chapter 3) and smaller than in six-coordinate octahedral [Fe(Ll)] (Chapter 4). The two +  other five-membered chelate ring angles (Nl(amine)-Re-N2(py) and NlA(amine)-ReN2A(py)) are 67.38(8)°, very similar to that of [Yb(Ll)N0 ]; however, the Ol-Re-Nl and 3  OTA-Re-N2A angles within the six-membered chelate rings are larger than the corresponding angles in [Yb(Ll)N0 ]. 3  The solution structures of the [ReO(L)] cations were studied by *H NMR +  spectroscopy. The spectra of pro-ligand H L1 and [ReO(Ll)]PF are shown in Figure 5.2. 2  6  The assignment of all hydrogens was aided by 'H-'H COSY spectrum of [ReO(Ll)]PF  6  - no-  References on p. 115  Chapter 5  shown in Figures 5.3. The complete assignment of all protons in all the complexes is presented in Table 5.2.  H /fH 2  4  H  e  DMSO  H,0  H,0  H /H 2  ii  8.5  i  i  i  Ii 8.0  i  i  ii  ii 7.5  i  i  i  i  i  7.0  i  i  i  i  i  6.5  i  i  i  I i  i  i  6.0  i  i  5.5  i i i iii ' i ii i  5.0  4.5  i  i  I 4.0  i  1111  iI  '  I '  3.5  i  '  I '  3.0  1  i  (ppm)  Figure 5.2. *H NMR spectra of pro-ligand H L1 in DMSO-ck (top), and of [ReO(Ll)]PF in 2  6  acetone-dt (bottom) (see p. 113 for labeling)  - Ill-  References on p. 115  Chapter 5  Figure 5.3. The -H--H COSY spectrum of [ReO(Ll)]PF in acetone-fife. 6  -112-  References on p. 115  Chapter 5  Table 5.2. H NMR Data (200 MHz) for the Re(V) Complexes in acetone-^. 1  Assignment  [ReO(Ll)]PF  [ReO(L2)]PF  [ReO(Ll)] [ReCl ]  H  3.61 (d, 2H)  3.65 (d, 2H)  3.40"  H '  4.26 (d, 2H)  4.28 (d, 2H)  4.14 (d, 2H)  H,  3.80 (d, 2H)  3.83 (d, 2H)  3.75 (d, 2H)  Hi'  4.63 (d, 2H)  4.64 (d, 2H)  4.52 (m, 2H)  H  2  6.31 (d, 2H)  6.34 (d, 2H)  6.32 (m, 2H)  H  3  6.95 (td, 2H)  6.96 (dd, 2H)  6.97 (t, 2H)  H  4  6.31 (t, 2H)  —  6.32 (m, 2H)  H  5  6.44 (d, 2H)  6.48 (d, 2H)  6.42 (d, 2H)  H  6  4.51 (d,2H)  4.54 (d, 2H)  4.52 (m, 2H)  H' 6  5.36 (d, 2H)  5.33 (d, 2H)  5.12 (d, 2H)  H  7  8.17 (d, 2H)  8.23 (d, 2H)  8.11 (d, 2H)  H  8  7.16 (t, 2H)  7.26 (td, 2H)  7.21 (t, 2H)  H  9  7.82 (td, 2H)  7.90 (td, 2H)  7.85 (t, 2H)  7.61 (d, 2H)  7.65 (d, 2H)  7.57, (d, 2H)  en  en  Hio  6  6  a  DMSO-rfg was used as the solvent.  b  This signal overlaps with residual H 0 in the solvent.  a  2  6  2  - 113 -  References on p. 115  Chapter 5  The equivalence of the pendant arms in the pro-ligand was maintained in the [ReO(L)] complexes.  H NMR spectra showed two sets of aromatic resonances  +  l  corresponding to the pyridine (H7-H10, 7.16-8.23 ppm) and oxybenzyl (H2-H5, 6.31-6.97 ppm) groups. In the pro-ligands, the ethylene (H ), and benzylic (Hi and He) protons appear en  as singlets at 2.70, 3.68, and 3.75 ppm, respectively (Figure 5.2). Upon coordination to the metal center, each of these signals become two doublets (Table 5.2). The simplicity of the !  H NMR spectra in the aromatic, benzylic and ethylene proton regions indicates the  symmetric nature of the monocationic [ReO(L)] complex in solution, similar to octahedral +  [Ga(L2)] and [In(L2)] , and to [ReO(bped)] at pD = 5.5. +  + 36  +  30  In conclusion, the oxorhenium(V) complexes with the potentially hexadentate ligands (H2LI and H2L2) have been synthesized from two routes: substitution of ReOCi3(PPli3)2 and aerial oxidation of K^fReCLj]. The X-ray crystallographic analysis of [ReO(Ll)] showed a +  symmetric seven-coordinate structure with a distorted pentagonal bipyramidal geometry. The solution structures of [ReO(L)] are similar to that in the solid state, as confirmed by the +  !  H NMR spectra. Both the solid state and solution structures are virtually identical to those  of [ReO(bped)] . °> + 3  31  - 114-  References on p. 115  Chapter 5  5.4. References  1)  Clarke, M.; Podbielski, L. Coord. Chem. Rev. 1987, 78, 253.  2)  Deutsch, E.; Libson, K.; Jurisson, S.; Lindoy, L. F. Prog. Inorg. Chem. 1983, 30, 75.  3)  Jurisson, S.; Desilets, C. P.; Jia, W.; Ma, D. Chem. Rev. 1993, 93, 1137 and references therein.  4)  Dilworfh, J. R.; Parrott, S. J. Chem. Soc. Rev. 1998, 27, 43 and references therein.  5)  Tisato, F.; Refosco, F.; Bandoli, G. Coord. Chem. Rev. 1994,135, 235.  6)  Technetium and Rhenium in Nuclear Medicine; Nicolini, M.; Bandoli, G.; Mazzi, U.,  Eds.; S. G. Editorali: Padova, 1995; Vol. 4 and references therein. 7)  Deklerk, J. M. H.; Vanhetschip, A. D.; Zonnenberg, B. A.; Vandijk, A.; Quirijnen, J. M. S. P.; Blijham, G. H.; Vanrijk, P. P. J. Nucl. Med. 1996, 37, 244.  8)  Bandoli, G.; Nicolini, M.; Mazzi, U.; Refosco, F. J. Chem. Soc, Dalton Trans. 1984, 2505.  9)  Jurisson, S.; Dancey, K. P.; McPartlin, M.; Tasker, P. A.; Deutsch, E. Inorg. Chem. 1984, 23, 4743.  10) Jurisson, S.; Lindoy, L. F.; Dancey, K. P.; McPartlin, M.; Tasker, P. A.; Uppal, D. K.; Deutsch, E. Inorg. Chem. 1984, 23, 227. 11) Tisato, F.; Refosco, F.; Mazzi, U.; Bandoli, G.; Dolmella, A. Inorg. Chim. Acta 1989, 164,127.  12) Tisato, F.; Refosco, F.; Mazzi, U.; Bandoli, G.; Nicolini, M. Inorg. Chim. Acta 1991, 189, 97.  13) Refosco, F.; Tisato, F.; Mazzi, U.; Bandoli, G.; Nicolini, M. J. Chem. Soc, Dalton Trans. 1988,611.  -115-  Chapter 5  14) Corlija, M.; Volkert, W. A.; John, C. S.; Pillai, M. R. A.; Lo, J. M.; Troutner, D. E.; Holmes, R. A. Nucl. Med. Biol. 1991,18, 167. Kothari, K.; Pillai, M. R. A. Appl. Radial hot. 1993, 44,9\\. Pillai, M. R. A.; John, C. S.; Lo, J. M.; Schlemper, E. O.; Troutner, D. E. Inorg. Chem. 1990,29, 1850.  Pillai, M. R. A.; Kothari, K.; Schlemper, E. O.; Corlija, M.; Holmes, R. A.; Volkert, W. A. Appl. Radiat. Isot. 1993, 44,1113.  Pillai, M. R. A.; John, C. S.; Lo, J. M.; Troutner, D. E.; Corlija, M.; Volkert, W. A.; Holmes, R. A. Nucl Med. Biol. 1993, 20, 211. Pillai, M. R. A.; Barnes, C. L.; Schlemper, E. O. Polyhedron 1994,13, 701.  Ramalingam, K.; Raju, N.; Nanjappan, P.; Linder, K. E.; Pirro, J.; Zeng, W.; Rumsey, W.; Nowotnik, D. P.; Nunn, A. D. J. Med. Chem. 1994, 37, 4155. Sugimoto, H.; Kamei, M.; Umakoshi, K.; Sasaki, Y.; Suzuki, M. Inorg. Chem. 1996, 35, 7082. Sugimoto, H.; Sasaki, Y. Chem. Lett. 1997, 541. Takahira, T.; Umakoshi, K.; Sasaki, Y. Acta Crystallogr., Sect. C1994, 50, 1870. Edwards, D. S.; Liu, S.; Poirier, M. J.; Zhang, Z.; Webb, G. A.; Orvig, C. Inorg. Chem. 1994, 33, 5607. Liu, S.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1991, 30, 4915. Liu, S.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1992, 31, 5400. Luo, H.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1993, 32, 4491. Luo, H.; Liu, S.; Rettig, S. J.; Orvig, C. Can J. Chem. 1995, 73, 2272. Luo, H.; Setyawati, I.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1995, 34,2287.  -116-  Chapter 5  30) Pierreroy, J.; M.Sc. Thesis; The University of British Columbia, 1997. 31) Xu, L.; Setyawati, I. A.; Pierreroy, J.; Rettig, S. J.; Orvig, C. Manuscript in preparation. 32)  Chatt, J.; Rowe, G. A. J. Chem. Soc. 1962, 4019.  33)  Watt, G. W.; Thompson, R. J. Inorg. Synth. 1963, 7, 189.  34) Botha, J. M.; Umakoshi, K.; Sasaki, Y.; Lamprecht, G. J. Inorg. Chem. 1998, 37, 1609. 35) Rouschias, G. Chem. Rev. 1974, 74, 531. 36)  Wong, E.; Liu, S.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1995, 34, 3057.  -117-  CHAPTER 6  Conclusions and Further Thoughts  6.1. General Conclusions The metal ions discussed in this thesis either play important roles in biological systems such as in metalloproteins, or have the potential to be diagnostic and/or therapeutic agents. The basic coordination chemistry of various metal ions (vanadium(IV), iron(III), rhenium(V) and lanthanides(III)) was explored, and biodistribution studies of a biologically active vanadium complex, bis(maltolato)oxovanadium(IV) (BMOV), and vanadyl sulfate (VS) using V tracer were presented. These studies represent some of the important steps in 4 8  the search for potent therapeutic or effective diagnostic agents which incorporate metal ions. Along with those obviously practical reasons, curiosity about how metal ions bind to different types of ligand was the impetus of the projects presented in this thesis. In Chapter 2, the stability constants of two oxovanadium(IV) complexes (BMOV and bis(kojato)oxovanadium(IV) (BKOV) were determined.  They have been proven to be  effective in enhancing insulin actions in vivo. ' BMOV was found to be slightly more stable 1 2  than BKOV. Due to the beneficial effects of BMOV in vivo, V biodistribution studies of 4 8  BMOV and its parent compound (VS) via oral or intraperitoneal administration in rats were carried out.  The data obtained from these studies were analyzed by compartmental  modeling. The results showed that the uptake of V from oral administration of V-BMOV 48  48  was approximately two to three times higher than that from an equivalent dose of VS, with 48  main localizations in bone, liver and kidneys. This higher uptake of V from an oral dose of 48  -118 -  References on p. 125  Chapter 6  AG  V correlated well with the two to three times greater potency of BMOV in lowering plasma glucose levels relative to that of VS.  1  Chapters 3, 4 and 5 discussed the complexation of Ln(III), Fe(III) and Re(V), respectively, by a potentially hexadentate ligand system (H2LI-H2L3). Due to a higher flexibility in coordination number and geometry of Ln(III) ions, three different types of complexes were formed. Neutral mononuclear complexes were obtained from the reaction of smaller Ln(III) (Dy-Lu) in the presence of sodium hydroxide; however, monocationic dinuclear complexes were produced from the same reaction involving larger Ln(III) (La-Gd). Changing the base to sodium acetate gave rise to the formation of monocationic trinuclear complexes. In a simple one step reaction, both mononuclear and dinuclear complexes can be easily converted to the trinuclear complexes. Basic coordination chemistry of iron(III) was investigated in Chapter 4.  The  intensely purple [Fe(Ll)] complex displayed an electronic spectrum similar to the model +  compounds of purple acid phosphatases, which contain a binuclear Fe(III) center. The X3  ray crystal structure of this complex showed a distorted octahedral geometry, similar to its Mn(III), Ga(III) and In(III) congeners. 4  5  Oxorhenium(V) complexes were synthesized from a ligand substitution reaction of Re OCl (PPh3)2 or from oxidation of Re(IV) to Re(V) in the presence of the pro-ligand. v  3  Similar structures were observed in solution and solid state, as shown by "H NMR and X-ray crystal structural analysis. Monocationic [ReO(Ll)] is seven coordinated with a distorted +  pentagonal bipyramidal geometry. This symmetric structure was maintained in solution, as proven by the simplicity of the "H NMR spectra.  -119-  References on p. 125  Chapter 6  In the Ln(III), Fe(III) and Re O complexes, aminopyridylphenolate ligands were v  coordinated to the metal centres in a hexadentate fashion. When the requirement of the metal ion coordination number was not satisfied, as in the Ln(III) complexes, the phenolate oxygen atoms of the ligand formed bridges, as did other smaller ligands (acetate) if they were present in the reaction solution. This mismatch between the ligand denticity and the coordination requirement of the metal ions can be utilized to build multinuclear complexes of different motifs.  6.2. Suggestions for Future Work In non-aqueous  solution, monocationic trinuclear Ln(III) complexes with  aminopyridylphenolate ligands were found to be stable based on the ease of the formation from mononuclear and dinuclear complexes and on the detection of stable high molecular weight parent peaks in the mass spectrometer. In order to provide a quantitative measure of the thermodynamic stability, aqueous solution studies of the Ln(III) complexes should be investigated by potentiometry.  The H2LI-H2L3 pro-ligands are not soluble in water;  however, sulfonation of the phenol rings increases water solubility considerably. The stability constants of Ga(III) and In(III) with sulfonated analogues have been reported.  6  Ln(III) complexes with polyaminocarboxylate ligands have been extensively studied in the search for effective contrast agents for MRI. ' Recently, Ln(III) complexes with 7 8  aminopyridylcarboxylate ligands have been studied in our group to see the effect of substituting acetate arms with pyridyl groups. Caravan et al. showed that neutral pyridyl 9  donors formed stable complexes and could be used as an alternative to neutral amide or alcohol oxygen donors.  -120-  References on p. 125  Chapter 6  As an extension of these studies on the effect of pyridyl donor atom in the coordination  with  Ln(III),  an  aminopyridylphenolate  with  (H2N6O2)  a  dien  (diethylenetriamine) backbone has been synthesized (Scheme 6.1, also see section 6.3). This diprotic pro-ligand is potentially octadentate with three tertiary amine nitrogen, three pyridyl nitrogen and two phenolate oxygen donor atoms. The product in each step was characterized by 'H NMR, mass specrometry and elemental analysis, whenever possible. The final product was isolated as brown sticky oil. Preliminary studies (LSIMS data) of Ln(III) complexes with this pro-ligand showed the presence of mononuclear [Ln(N6C»2)] complexes. +  A  thorough study of this complexation will provide a better picture in understanding the effects of adding pyridyl groups in pro-ligands. In Chapter 4, the crystal structure of [Fe(Ll)] exhibits two phenolate oxygen atoms +  cis to each other, which can potentially form bridges to another metal ion, such as Ln(III), in future  heteromultinuclear  complexes.  Investigating  other  3d-metal  ions with  aminepyridylphenol pro-ligands, and subsequently with Ln(III), will broaden our horizon in the area of multinuclear complex architecture. Studies on the  99/99m  T c congeners of [ReO(Ll)] are worth pursuing to investigate +  complexes with the widely used radionuclide ( Tc) for potential medical imaging agents. 99m  Tc complexes with aminopyridylphenolate ligands could then be compared with previously studied Tc complexes with aminopyridine (H pmen), aminopyridylcarboxylate (H bped)  10  2  2  and aminophenolate ligands.  11  -121 -  References on p. 125  Chapter 6  H bpdien.3HCl 2  i  HN0 2  6  2  Scheme 6.1.  - 122 -  References on p. 125  Chapter 6  6.3.  Preparation of  H2N6O2  (l,7-bis(2-hydroxybenzyI)-l,4,7,-tris(2-methylpyridyl)-  1,4,7-triazaheptane)  Materials. In addition to those listed in section 3.2., diethylenetriamine was obtained from Aldrich, and was used without further purification. Instrumentation. As described in sections 3.2, and 5.2. Synthesis  H bpdien»3HCl. 2  of  l,7-bis(2-hydroxybenzyl)-l,4,7-triazaheptane  trihydrochloride,  The procedure is similar to that reported previously, with some 12  modifications. To a hot solution of diethylenetriamine (dien, 5.18 g, 50.2 mmol) in 35 mL ethanol, salicylaldehyde (13.5 g, 111 mmol) was added dropwise; the mixture turned yellow immediately. After stirring at 50 °C for 2 h, the solution was cooled to room temperature. After a slow addition (over a 1.5 h period) of NaBH (4.12 g, 109 mmol) at room 4  temperature, the stirring was continued at 50 °C for another 2 h. The resulting cloudy yellow solution was then cooled to room temperature, and the solvent was removed under reduced pressure leaving yellowish solid residue. The aqueous mixture of this residue was extracted with 3 x 50 mL CH2C1 . The combined organic layer was dried over anhydrous MgSC»4, 2  filtered, and the solvent was removed on a rotary evaporator yielding yellow oil. It was dissolved in 1 M HC1 (75 mL), and the solvent was then removed in vacuo. Ethanol (50 mL) was added to the yellow oil yielding the formation of white precipitate. The product was collected by filtration, yield 8.2 g (52%). Anal. Calcd. (found) for C-8H28CI3N3O2: C, 50.89 (50.80); H, 6.64 (6.63); N, 9.89 (9.64). H NMR (200 MHz, D 0): 3.45 (m) (8 H ); 4.25 (s) !  2  en  (4 benzylic H); 6.95 (m), 7.35 (m) (8 aromatic H).  - 123 -  References on p. 125  Chapter 6  Synthesis triazaheptane,  of  H2N6O2.  l,7-bis(2-hydroxybenzyl)-l,4,7,-tris(2-methylpyridyl)-l,4,7To a mixture of H2bpdien»3HCl (2.1 g, 5 mmol) and 2-picolyl  chloride hydrochloride (2.5 g, 16 mmol) in 20 mL of H2O, an aqueous NaOH solution (~ 4 M) was added to raise the pH to 8. Methanol (10 mL) was added, and the pink mixture was stirred at room temperature for 4 days. The pH was kept at around 8-10 with further additions of an aqueous NaOH (the total of NaOH used in all additions was 1.84 g, 46 mmol) and more methanol was added (22 mL). The resulting mixture was orange with a suspended brown oil. The solvent was removed under pressure leaving a brown oily residue. It was dissolved in 50 mL CHCI3, and the organic layer was washed with H2O. The organic layer was separated from the aqueous layer, and the solvent was removed in vacuo, yielding a brown sticky oil (2.8 g, 95%). LSIMS: m/z = 598 ([L+l] ). H NMR (200 MHz, CDC1 ): +  !  3  2.57 (s) (8 H ); 3.48 (s), 3.56 (s), 3.62 (s) (10 benzylic H); 6.60-7.20 (m), 7.32-7.5 (m), 8.35 en  (d), 8.45 (d) (20 aromatic H).  - 124 -  References on p. 125  Chapter 6  6.4. References  1)  Yuen, V. G.; Orvig, C.; McNeill, J. H. Can. J. Physiol. Pharmacol. 1995, 73, 55.  2)  Yuen, V. G.; Caravan, P.; Gelmini, L.; Glover, N.; McNeill, J. H.; Setyawati, I. A.; Zhou, Y.; Orvig, C. J. Inorg. Biochem. 1997, 68, 109.  3)  Krebs, B.; Schepers, K.; Bremer, B.; Henkel, G.; Althaus, E.; Muller-Warmuth, W.; Griesar, K.; Haase, W. Inorg. Chem. 1994, 33, 1907.  4)  Neves, A.; Erthal, S. M. D.; Vencato, I.; Ceccato, A. S.; Mascarenhas, Y. P.; Nascimento, O. R.; Horner, M.; Batista, A. A. Inorg. Chem. 1992, 31, 4749.  5)  Wong, E.; Liu, S.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1995, 34, 3057.  6)  Wong, E.; Caravan, P.; Liu, S.; Rettig, S. J.; Orvig, C. Inorg. Chem. 1996, 35, 715.  7)  Watson, A. D. J. Alloys Compd. 1994, 207/208, 14.  8)  Kumar, K.; Jin, T.; Wang, X.; Desreux, J. F.; Tweedle, M. F. Inorg. Chem. 1994, 33, 3823.  9)  Caravan, P.; Mehrkhodavandi, P.; Orvig, C. Inorg. Chem. 1997, 36, 1316.  10) Pierreroy, J.; M.Sc. Thesis; The University of British Columbia, 1997. 11) Wong, E.; Ph.D. Thesis; The University of British Columbia, 1996. 12) Ma, R; Murase, I.; Martell, A. E. Inorg. Chim. Acta 1994, 223, 109.  -125-  APPENDICES  Table A l . Biodistribution of V-BMOV Oral Administration in Rats. (Experiment A - n=3, %AD/gram organ, mean (SD)) Organ  15 min  30 min  1h  4h  24 h  Blood  0.053 (0.019)  0.070 (0.050)  0.113 (0.066)  0.235 (0.213)  0.039 (0.005)  Liver  0.053 (0.027)  0.045 (0.022)  0.077 (0.031)  0.163 (0.149)  0.063 (0.009)  Kidneys  0.066 (0.039)  0.041(0.018)  0.104 (0.054)  0.363 (0.253)  0.251 (0.074)  Spleen  0.161 (0.118)  0.041 (0.014)  0.078 (0.071)  0.075 (0.051)  0.078 (0.011)  Lung  0.138 (0.154)  0.057 (0.030)  0.106 (0.081)  0.121 (0.101)  0.043 (0.003)  Heart  0.062 (0.020)  0.058 (0.007)  0.068 (0.034)  0.073 (0.046)  0.053 (0.007)  Brain  0.165 (0.184)  0.041 (0.003)  0.039(0.031)  0.015 (0.005)  0.023 (0.003)  Testes  0.019 (0.002)  0.018(0.004)  0.025 (0.011)  0.040 (0.028)  0.027 (0.003)  6.45 (1.90)  5.84(1.72)  1.91 (0.82)  0.51 (0.13)  0.048 (0.010)  Bone  0.205 (0.106)  0.136 (0.056)  0.167 (0.098)  0.296 (0.087)  0.323 (0.074)  Muscle  0.034 (0.012)  0.023 (0.001)  0.040 (0.015)  0.038 (0.024)  0.025 (0.003)  Stomach  - 126-  Appendices  Table A2. Biodistribution of VS Oral Administration in Rats. (Experiment A - n=3, %AD/gram organ, mean (SD)) Organ  15 min  30 min  1h  4h  24 h  Blood  0.058 (0.052)  0.057 (0.012)  0.049 (0.025)  0.138 (0.049)  0.015 (0.009)  Liver  0.104 (0.059)  0.039 (0.008)  0.048 (0.014)  0.097 (0.029)  0.020 (0.008)  Kidneys  0.049 (0.018)  0.035 (0.013)  0.045 (0.027)  0.274 (0.101)  0.057 (0.023)  Spleen  0.082 (0.020)  0.063 (0.020)  0.059 (0.053)  0.050 (0.018)  0.023 (0.005)  Lung  0.093 (0.021)  0.034 (0.004)  0.056 (0.050)  0.084 (0.046)  0.013 (0.002)  Heart  0.127 (0.014)  0.035 (0.009)  0.044 (0.029)  0.058 (0.021)  0.016 (0.003)  Brain  0.147 (0.041)  0.036 (0.013)  0.020 (0.006)  0.025 (0.001)  0.007 (0.002)  Testes  0.059 (0.048)  0.014 (0.001)  0.028 (0.009)  0.026 (0.009)  0.010 (0.002)  17.75 (4.72)  2.23 (0.91)  4.11 (2.06)  1.30 (0.54)  0.015 (0.004)  Bone  0.133 (0.017)  0.156 (0.045)  0.060 (0.054)  0.176 (0.091)  0.088 (0.026)  Muscle  0.094 (0.046)  0.025 (0.004)  0.036 (0.012)  0.030 (0.006)  0.010(0.001)  Stomach  - 127-  Appendices  00 1-H  o Tf  CN  43  ON  co in CN  a  Q  o  1  00  ©  ©  i—«  m VO  Tf  d  d  no oo ro  CN  ON  d  o d  O d  O d  o d  o  00  ON ON  to ro d  d  CN i—i  Tf  Tf  CN  d  d  m  vo vo  ro  ON  o d  o d  in o  in  o in  CN  d  d  d  vo  ON  o d  i—i  Tf  ON  00  vo  o d  CO vo  CO  o d  Tf  oo  o d  1-H  o d  i—<  Tf  CN  o d  i—i  CN d  i—i  Tf  o d  o  vo CN O d  <o vo  00  d  d  d  d  d  00 00 o d  ro ro O  Ti-  m  Tf  ro  00  d  o d  o d  in  ON CN  ro O d  00 o d  o  vo CN  ro vo  d  d  d  ON  ro  d  i—i  CN O  o d  i-H  i—<  O d  CO  o d  ON  o d  O d  o  o o d  1—H 1—H  ON  d  d  d  o o d  ro o  o  r-  o >—i  m o  o  o d  vo  ON  o d  o  o d  O d  00  o d  o o d  o d  o d  O O  ON ro O d  o d  vo  ro vo  vo CN  d  T-H  o d  vo d  o d  d  1—H  in Os uo  i—l d  00  d  ro O  CN  Tf  d  o  CN o  o  ON  00 r~ 00 d  ON  o d  m  O d  o d  o d  Ti-  CN  o o  CN CN  Tf  ro CN  o © d  o d  i—i  O  oo  VO vo  o d  1-H  CN  Tf  ON  o  d  1-H  ON  in  m o o d  00 © o d  o o d  CN  d  CN O 00 o d  o o d  in  CN O  m  o d  o d  i—<  vo m o d  ro  O  CN  o d  Ti-  vo  d  o d  *—i  i—i  Tf  CO  m  CN CN  oo  CO  00  o  m  o o d  i—i  d  ro d  00 o d  d  ON Tf  CN d  m  00  o d  d  1-H  CN VO  S in  T3  CN  o d  ©  CO  43 O  o  ON Tf  vo  ON  Tf  VO CO  i—i  d  43  00  tJO  43  VO  o d  ro vo o d  ON  O d  00  © d  i>  CN O d  CO ON  o d  in  VO  00  ON  d  O d  o d  o d  00  ro  i-H  o d  o  i—H  1-H  d  Tf  Tf  m  m in  vo  © d  Tf  o d  1-H  o d  o d  CN ro  00  O d  O d  00  ro VO  d  d  ON  Tf  Tf  i—  d  d  T-H  ro  CN  1-H  00  i—t  1-H  o  o d i—t 1-H  o d  1  m  00 o d  ro vo >— 1  d  Q i-H ON  ON  >  o  vo 43  d  d  d  o d  CN  o  Tf  in  _^  T  a I  a co  ro CN d  -2  S  .2  £  in  T3  o  o o CQ  CN CN d  ON 1-H  d  CO  >  J  s  T3  ^  ON  o d  S3  u  "E,  CN VO o o  m r»» o d  ON Tf  o ©, Tf  vo o d  CO  co o d  ^—^  CN Tf  O d  m o o d o o d  ro CN O d s  —-'  Tf  CN O d  o 00  ON  d  d  CN  oo o  i—  1  rrd  O i—  1  i-H  d  m  VO  o d  ro  i-H  1-H  d  vo  CN  o d  ro  CN  i-H  d  43  C/3  00  C/3  cS )H  CQ  GO  - 128-  C/3  H  s O  ^H  CO  S3  o CQ  CO a "3  •c  Appendices  - 129-  Appendices  Table A5. Biodistribution of V-BMOV i.p. Administration in Rats. (Experiment C - n=3, %AD/gram organ, mean (SD)) Organ  15 min  30 min  lh  4h  Blood  0.292 (0.321)  0.746 (0.169) 0.502 (0.353) 0.150 (0.222) 0.075 (0.052)  Liver  0.179 (0.215)  0.490 (0.205) 0.358 (0.205) 0.146 (0.220) 0.148 (0.144)  Kidneys  0.267 (0.294)  1.430(0.582)  Spleen  0.207 (0.258)  0.563 (0.360) 0.311 (0.233) 0.145 (0.213) 0.164 (0.157)  Lung  0.149 (0.168)  0.458 (0.157) 0.256 (0.176) 0.093 (0.131) 0.060 (0.045)  Heart  0.083 (0.065) 0.254 (0.061) 0.164 (0.093) 0.072 (0.083) 0.058 (0.028)  Brain  0.021 (0.013) 0.046 (0.016) 0.037(0.016)  Testes  0.031 (0.018) 0.147 (0.042) 0.104 (0.073) 0.059 (0.074) 0.047 (0.038)  Bone  0.137(0.123)  0.718(1.18)  1.596 (0.582)  0.016(0.013)  24 h  0.615 (0.673)  0.018(0.007)  0.738 (0.273) 0.782 (0.617) 0.542 (0.878) 0.887 (0.925)  Table A6. Biodistribution of VS i.p. Administration in Rats. (Experiment C - n=3, %AD/gram organ, mean (SD)) Organ  15 min  30 min  4h  24 h  Blood  0.434 (0.378)  0.591 (0.508)  0.092 (0.148)  0.099 (0.079)  Liver  0.343 (0.287)  0.340 (0.297)  0.137(0.226)  0.228 (0.192)  Kidneys  0.750 (0.645)  0.971 (0.840)  0.971 (1.29)  1.082 (0.926)  Spleen  0.487 (0.414)  0.488 (0.404)  0.488 (0.064)  0.168 (0.132)  Lung  0.287 (0.258)  0.373 (0.298)  0.050 (0.075)  0.092 (0.074)  Heart  0.174 (0.122)  0.219(0.162)  0.046 (0.060)  0.072 (0.049)  Brain  0.0304 (0.015)  0.036 (0.015)  0.009 (0.008)  0.017 (0.007)  Testes  0.071 (0.071)  0.110(0.070)  0.034 (0.047)  0.062 (0.046)  Bone  0.301 (0.241)  0.633 (0.537)  0.535 (0.894)  1.449(1.235)  - 130-  Appendices X  o  ro  X CJ  O fN  o  vq  CJ  co •  X CJ  o  ro  s  ro  X CJ •  o z  loo  q ro rr-  a  fN VO  o  m CN ©  ON  r-  o  /-^  Tf  c  ro co  o  o c  mo  O K m  Tf  CN  CN in T-H  T-H  vo  CN m CN CN  © CN  ON ON  00  ^ — ^  T-H  O in  CO 00 00  CN CN  o  ON  © © © ©  CN © in  ON'  r-  vq  ©•  CN r-  T-H  00  ON  Tf  CN  T-H  CO oo  ©  CN  ©  © ©  © ©  Tf  Tf  a o  ro  a CJ  o o u  ro  a CJ CO  O  a o tf  CJ in •  o  ro  O  •  CO  a o tf  CJ  O oz  , —  CJ  T ?  CQ 00  oo  a  o CJ  a  o  o z  CN CO ©  CN CN CN  S  0\ 1—*  'S t3  PH  © CO t-; CO  CN  o( m m  T-H - H  — 'i  r—s  in  T-H  ^ 0 0-^  Tf_  ON  ON  co © T-H  vq  r00 Tf  00 1—1 T-H  ©^  r-  CN  00 00  00  VO VO  00  T-H  CN ON  VO CN © 1—<  '  1  © © © © in [—  ©  Tf  in CO 00  CN  " H —  oo  in in  o  A  [£  a  vo  tf o  "o ON  CN  Tf  o c o  £  c--  T-H  ©^ m  T—H  ON  in  CN  1-H  00  CN PH  00 T-H  CN  CO  o'  Tf •—  ON'  ON  VO ©  1  CN CN  Tf  rco ©  ON  vo  Tf  CN © ©  CN © ©  CN CO © ©  © CO © ©  2<  af  m ©  in ©  Tf^  00 00  VO  CN  © © © ©  CN  CN  vo 00  VO  Tf  o o  in  ON  m  in © vq Tf  T-H'  m rCN CO  vo  CN ©  CN  O g  ro  O oa CN  PH  O  tf o  •  o z  fN  6  ©  tf r-  o  00 fN  CJ  X  3  O  r-  i-H  VO T-H  i3  PH  T-H  CN CN Tf  ©  CN CO  T T-H H  T »-H H  00  o  CO CN  CO  O^  ON  CN CO T-H  CN  OO T-H  Tf  (--  CN T-H  ^ — ^ T-H  VO in CO 00  t-in ON  CO  00  CN CN  T-4  ©  vq  00  CN  CN r-;  r~  £ o  © vq oo vo  ©  43  o o  CN CN CN  CJ  CN VO in in 00  00  vo  VO m  r-  oo '—i  VO  T-H  CN  m  ON  Tf  CO  VO CN  '—i  1-H  ON ON  in CO  o  00  u o  VO ©  1—i  Tf' Tf CO  E  I. a O-  m  00 00  © © © ©  40  O a  Ia  r-ON  43 >* fN  "5. £  © © © ©  PH  T3  60 T3  «3  131 -  ^£  60  -a  N  1 ° vt =C  ©  T-H T-H  ©  I  05  Appendices  Table A8. Bond Lengths (A) and Bond Angles (deg) for [Yb(Ll)N0 ] 3  atom.  atom  distance  atom  atom  distance  Yh(l)  0(1)  2.163(4)  Yb(l)  0(2)  2.432(4)  Yb(l)  Nd)  2.504(4)  Yb(l)  N(2)  2.508(4)  0(1;  C(4)  1.308(6)  0(2)  N(3)  1.276(5)  0(3)  N(3)  1.225(7)  N(D  C(l)  1.486(7)  N(U  0(2)  1.490(6)  N(l)  0(9)  1.482(8)  N(2)  C(10)  1.332(7)  N(2)  0(14)  1.367(7)  C(l)  C(D*  1.504(11)  C(2)  0(3)  1.501(8)  CY3)  C(4)  1.403(9)  C(3)  0(8)  1.401(8)  C(4)  0(5)  1.414(8)  0(5)  0(6)  1.394(8)  •v V'  0(7)  :  1 411(9) 1 ' T i l X^&,;J  C{9;  C(10)  1.517(9)  C(10)  0(11)  1.391(7)  C(ll)  0(12;  1.366(9)  C(12)  0(13)  1.356(9)  C(13)  C(14)  1.394(8)  *Here and elsewhere, symmetry operation: 1-x, y, 1/2-z  - 132-  Appendices  Table A8. Continued atom  atom  atom  angle  atom  atom  atom  angle  0(1)  Ybfl)  0(1)*  156.3(2}  0(1)  Yb(l).  0(2)  128.19(14)  0(1)  Vb(l)  0(2)*  75.49(14)  0(1)  Yb(l)  N(D  77.65(14)  0(1)  Vb(l)  N(l)*  83.11(14)  oci)  Yb(l)  N(2)  98.78(15)  0(1:  Yb(l)  N(2;«  86.25(14)  0(2)  Yb(l)  0(2)*  53.1(2)  0(2)  Yb(l)  N;I)  141.15(14)  0(2)  Yb(l)  N(D*  132.40(14)  0(2)  Yb{i)  N;2)  79.17(15)  0(2)  Yb(l)  N(2)»  78.93(15)  N(D  Yb{l)  N(D*  71.4(2)  N(l)  Yb(l)  N(2)  67.26(15)  Nti]  Yb(l)  N(2)*  137.01(15;  N(2)  Yb(l)  N(2)*  155.5(2)  Yb(l')  0(1)  C{4)  139.1(1)  Yb(l)  0(2)  N(3)  95.0(3)  Vb:li  Nil)  C(l)  111.3(3}  Yb',1)  N(l)  C(2)  112.3(3)  Yb(i;  N;D  C(9)  105.9(4)  C(l)  Nil)  C(2)  111.8(4)  Cd)  N(l)  C(9)  108.4(4)  C(2)  N(l)  0(9);  106.8(4)  VbU)  N;2;  C(10)  116.0(4)  Yb(l)  N(2)  C(14)  125.8(4)  C(10)  N(2)  0(14)  118.1(5)  0(2)  N.(3)  0(2)*  116.8(6)  0(2)  N(3)  0(3)  121.0(3)  N(D  C(l)  C(D*  112.6(4)  N(l)  C(2.)  C(3)  1164(5)  C(2)  C(3)  0(4)  119.3(6)  C(2j  C(3;  C(8)  119.5(6)  C(4)  C(3)  0(8)  121.1(6)  0(1)  C(4)  C(3)  120.8(5)  0(1)  C(4)  0(5)  121.0(5}  0(3)  C(4)  0(5)  118.2(5)  C(4)  0(5)  C(6)  120.6(6)  C{5)  C(6)  C(7)  120.8(6)  C(6)  C(7)  C(8)  119.9(6)  cm  C(S)  C(7)  119.4(6)  N(D  C(9)  C(10)  111.0(5)  N(2):  C(10)  C(9)  116.7(5)  N(2)  C(10)  C(H)  121.9(6)  C(9)  C(10)  C(ll)  121.4(6)  C(10)  C(ll)  C(12)  119.3(6)  0(1.1)  C(12)  C(13)  120.3(7)  C(12)  C(13)  0(14)  118.5(6)  N"(2)  C(14)  0(13)  121.8(6)  ;  - 133 -  Appendices  Table A 9 . Bond Lengths (A) Bond Angles (deg) for [Pr (Ll)2(N03)(H20)][N03]'CH OH. 2  3  atom atom distance  atom atom distance  atom  atom distance  atom  atom distance  Pr(l) 0(2) 2.400(2)  Pr(l) 0(1) 2.309(2)  C(l)  C(2) 1.504(4)  C(3)  C(4)  1.496(4)  Pr(l) 0(4) 2.483(2)  Pr(l) 0(3) 2.426(2)  C(4)  C(5) 1.386(4)  C(5)  C(6)  1.374(5)  Pr(l) N(2) 2.796(2)  Pr(l) N(l) 2.720(2)  C(6)  C(7) 1.372(5)  C(7)  C{8)  1.398(4)  Pr(l) N{4) 2.717(2)  Pr(l) K(3) 2 690(2)  C(9)  C(10) 1.514(4)  C(10) C(ll) 1.420(4)  Pr(2) 0(4) 2.446(2)  Pr(2) 0(3) 2,377(2)  C(10) C(15) 1.389(4)  C(ll) C(12) 1.404(4)  Pr(2) 0(6) 2.588(2)  Pr(2) 0(5) 2.588(2)  C(12) C(13) 1.382(4)  C(13) C(14) 1.376(4)  Pr(2) N(5) 2.712(2)  Pr(2) 0(8) 2448(2)  C(14) C(15) 1.386(4)  C(16) C(17) 1.510(4)  Pr(2) N(7) 2.643(2)  Pr(2) K(6) 2.717(3)  C(17) C(18) 1.390(4)  C(18) C(19) 1.397(5)  0(1) C(ll) 1,324(3)  Pr(2) N(8) 2.652(3)  C(19) C(20) 1.366(5)  C(20) C(21) 1.387(5)  0(3) C(39) 1.361(3)  0(2) C(24) 1.336(3)  C(22) C(23) 1.510(4)  C(23) C(24) 1.400(4)  0(5) N(9) 1.256(3)  0(4;  C(23) C(2S) 1 405(4)  C(24) C(25) 1.410(4)  0(7) N(9) 1,228(3)  0(6) N(9) 11277(3)  C(25) C(26) 1.379(5)  C(26) C{27) 1.389(5)  0(10) N(10) 1.245(3)  0(9) 'N(IO) 1.235(4)  C(27) C(28) 1.397(5)  C(29) C(30) 1.524(4)  0(12) C(57) 1.369(6)  0(11) N(10) 1.246(4)  C(31) C(32) 1.507(4)  C(32) C(33) 1.402(4)  N(l) C(3) 1.480(4)  N(l) C(l) 1478(4)  C(33) C(34> 1.363(5)  C(34) C(35) 1.390(5)  N(2) C(2) 1.487(4)  N(l) C(9) 1484(4)  C(35) C(36) 1.392(4)  C(37) C(38) 1.497(4)  N(2) C(22) 1.496(4)  N(2) C{16) 1.479(3)  C(38) C(39) 1.410(4)  C(38) C(43) 1.389(4)  N(3) C(8) 1.346(4)  N(3) C(4) 1.358(4)  C(39) C(40) 1.381(4)  C(40) C(41) 1.387(4)  N(4) C(21) 1.349(4)  N(4) C(17) 1.338(4)  C(41) C(42) 1.381(4)  C(42) C(4?) 1.384(5)  N(S) C(31) 1.479(3)  N(5) C(29) 1.486(4)  C(44) C(45) 1.516(4)  C(45) C{46) 1.376(5)  N(6) C(30) 1.492(4)  N(5) C(37) 1.497(4)  C(46) C(47) 1.380(5)  C(47) C(48) 1.383(6)  N(6) C(50) 1.524(3)  N(6) C(44) 1:475(4)  C(48) C(49) 1.377(5)  C(50) C(51) 1.5H(')  N(7) C(36) 1.337(4)  N(7) C(32) 1.347(4)  C(51) C(52) 1.399(4)  C(51) C(56) '..394(4)  N(8) C(49) 1.353(4)  N(8) C(45) 1.337(4)  C(52) C(53) 1.401(4)  C(53) C(54) 1.392(4)  C{54) C(55) 1.379(5)  C(55) C(56) 1.396(5)  C(52) 1.353(3)  - 134-  Appendices  Table A9. Continued. atom  atom  atom  angle  atom  atom  atom  angle  Pr(l)  O(l)  C(ll)  147.3(2)  Pr(l)  0(2)  C(24)  133.4(2)  Pr{l.)  0(3)  Pr(2)  113.71(7)  Pr(D  0(3)  C(39)  119.7(2)  Pr(2)  0(3)  126.52(15)  Pr(l)  0(4)  Pr(2)  109.31(7)  0(4)  C(52)  132.9(2)  Pr(2)  0(4)  C(52)  117.2(2)  0(51  N(9)  96.6(2)  Pr(2)  0(6)  NO)  96.2(2)  N(l)  C(l)  109.6(2)  Pi(l)  K(l)  C(3)  106.2(2)  Pr(l).  N{1)  C(9)  113.44(14)  C(l)  N(l)  C(3)  110.4(2)  C(l)  NU,  C(9)  108.6(2)  C(3)  N(l)  C(9)  108.5(2)  Pr(l)  N(2)  C(2)  110.7(2)  Pr(l)  N(2)  C(16)  109.17(15)  Fr(l)  N(2)  C(22)  110.3(2)  C(2)  N(2)  C(16)  108.0(2)  C(2)  N(2)  C(22)  108.6(2)  C(16)  N(2)  C(22)  110.1(2)  Pr(l)  N(3)  C(4)  118.2(2)  Pr(l)  N(3)  C(8)  124.2(2)  C(4)  N(3)  C(8)  117.4(2)  Pr(D  N(4)  C(17)  121.2(2)  Pr(l)  N(4)  C{21)  121.3(2)  C(17)  N(4)  C(21)  117.5(3)  Pr(2)  N(5)  C(29)  106.3(2)  Pr(2)  N(S)  C(31)  110.4(2)  Pr(2)  N(5)  C(37)  112.37(14)  C(29)  N(5)  C(31)  108.0(2)  C(29)  N(5)  C(37)  110.1(2)  C(31)  N(5)  C(37)  109.6(2)  Pr(2)  N(6)  C(30)  111.3(2)  Pr(2)  N(6)  C(44)  107.9(2)  Pr(2)  N(6)  C(50)  111.78(15)  C(30)  N(6)  C(44)  108.0(2)  C(30)  N(6)  C(50)  105.4(2)  C(44)  N(6)  C(50)  112.5(2)  Pr(2)  N(7)  C(32)  119.5(2)  Pr(2)  N(7)  C(36)  120.7(2)  C(32)  N(7)  C(36)  118.1(3)  Pr(2)  N(8)  C(45)  118.7(2)  Pr(2)  N(6)  C(49)  122.6(2)  C(45)  N(8)  C(49)  118.1(3)  0(5)  N(9)  0(6)  117.4(2)  0(5)  N(9)  0(7),  121.5(3)  0(6)  N(9i  0(7)  121.1(3)  O(Q)  N(10)  O(10)  120.0(3)  NilO)  O(ll)  120.5(3)  O(10)  N(10)  O(ll)  119.4(3)  N(l)  Cd)  C(2)  112.3(2)  N(2)  C(2)  C(l)  112.6(3)  N(l)  Ci'3)  C(4)  111.4(2)  N(3)  C(4)  C(3)  115.8(2)  iiiiii  C(4)  C(5)  1224(3)  C(3)  C(4)  C(5)  121.6(3)  C(5)  C(6)  119.2(3)  C(5)  C(6)  C(7)  119 7(3)  C(6)  C(7)  C(8)  118.5(3)  N(3)  C(8)  C(7)  122 6(3)  NO)  C(9)  C(10)  116.7(3)  C(9)  C(10)  C(ll)  122.0(3)  C(9).  C{10)  C(15)  118.4(3)  C(l.l)  C(10)  C(15)  119.4(3)  Pi(2)  0(9)  '  -135 -  Appendices  Table A9. Continued atom  atom  atom  angle  atom  Pr(l)  O(l)  C(J1)  147.3(2)  Pr(l)  0(3)  Pr(2)  113.71(7)  Pr(2)  :  prfp:;;l  0(3)  llliQ(3?)  0(4)  C(52)  0(5) N(l)  C(l)  atom  angle  0(2)  C(24)  133.4(2)  Pr(D  0(3)  C(39)  119.7(2)  126.52(15)  Pr(D  0(4)  Pr(?)  109.31(7)  132.9(2)  Pr(2)  0(4)  C(52)  117.2(2)  96.8(2)  Pi(2)  0(6)  N(9)  96.2(2)  109 6(2)  Pr(l)  N(D  C(3)  106.2(2)  113 44(14)  C(l)  N(l)  C(3)  110.4(2)  : atom:  Pr(l')  NO)  C(l)  N(l)  C(9)  108.6(2)  C(3)  N(l)  C(9)  108.5(2)  Pr(l)  N(2)  C(2)  110.7(2)  Pr(l)  N(2)  C(16)  109.17(15)  Pr(D  N(2)  C(22)  110.3(2)  C(2)  N(2)  C(16)  108.0(2)  C(2)  N(2)  C(22)  108.6(2)  C(16)  N(2)  C(22)  no:i(2)  Pr(l)  N(3)  C(4)  118.2(2)  Pr(l)  N(3)  C(8)  124.2(2)  C(4)  N(3)  C{8)  117.4(2)  Pr(D  N(4)  C(17)  121,2(2)  Pr(l)  N(4)'  C(21)  121.3(2)  C(17)  N(4)  C(21)  117.5(3)  Pr<2)  N(5)  C(29)  106.3(2)  Pr(2)  N(5)  C(31)  110.4(2)  Pr(2)  N(5)  C(37)  112.37(14)  C(29)  N(5)  C(31)  108.0(2)  C(29).  N(5)  C(37)  110.1(2)  C(31)  N{5)  C(37)  109.6(2)  Pr(2)  N(6)  C(30)  111.3(2)  Pr(2)  N(6)  C(44)  107.9(2)  Pr(2)  N(6)  C(50)  111.78(15)  C(30)  N(6)  C(44)  108.0(2)  C(30)  N(6)  C(50)  105.4(2)  C(44)  N(6)  C(50)  112.5(2)  Pr(2)  N(7)  C(32)  119.5(2)  Pr(2),  N(7)  C(36)  120.7(2)  C(32j  N(7)  C(36)  118.1(3)  Pr(2)  N(8)  C(45)  118.7(2)  Pr(2)  N(6)  C(49)  122.6(2)  C(45)  N(8)  C(49)  118.1(3)  Q(5)  NJ9)  0(6)  117.4(2)  0(5)  N(9)  0(7)  121.5(3)  0(6)  Nl9)  0(7)  121.1(3)  0(9)  N(10)  0(10)  120.0(3)  0(9)  NMO)  O(ll)  120.5(3)  0(10)  N(10)  O(ll)  119.4(3)  N(1J  Cd)  C(2)  112.3(2)  N(2)  C(2)  C(l)  112.6(3)  N(l)  C(3)  C(4)  1114(2)  N(3)  C(4)  C(3)  115.8(2)  N{3)  C(4)  C(5)  122.4(3)  C(3)  C{4)  C(5)  121.8(3)  C(4)  C(5)  C(6)  119.2(3)  C(5)  C(6)  C(7)  119.7(3)  C(6)  C(7)  C(8)  118.5(3)  N(3)  C(8)  C(7)  122.8(3)  N(l)  C(9)  C(10)  116.7(3)  C(9)  C(10)  C(ll)  122.0(3)  C(9)  C(10)  C(15)  118.4(3).  C(ll)  C{10).  C(15)  119.4(3)  - 136-  Appendices  Table A9. Continued atom  atom  atom  angle  atom  O(l)  C(ll)  C(10)  120.8(3)  C(10)  C(ll)  C(12)  C(12)  C(13)  C(10)  angle  O(l)  atom C(ll)  atom C(12)  122.3(3)  117.0(3)  C(ll)  C(12)  C(13)  122.0(3)  C(14)  120.8(3).  C(13)  C(14)  C(15)  118.3(3)  C(15)  C(14)  122.4(3)  N(2)  C(16)  C(17)  111.9(2)  N(4)  C(17)  C(16)  116.8(3)  N(4)  C(17)  C(18)  122.9(3)  C(16)  C(17).  C(18)  120.3(3)  C(17)  C(18)  C(19)  118.6(3)  C(18)  C(19)  C(20)  118.8(3) .  C(19)  C(20)  C(21)  119.2(3)  N(4)  C(21)  C(20)  122.9(3)  N(2)  C(22)  C(23)  114.4(2)  C(22)  C(23)  C(24)  120.9(3)  C(22)  C(23)  C(28)  119.5(3)  C(24)  C(23)  C(28)  119.7(3)  0(2)  C(24)  C(23)  120.5(3)  0(2)  C{24)  C(25)  121.5(3)  C(23)  C{24)  C(25)  118.0(3)  C(24)  C(25)  C(26)  121.7(3)  C(25)  C{26)  C(27)  120.6(3)  C(26)  C(27)  C(28)  118.5(3)  C(23)  C(28)  C(27)  121.4(3)  N(5)  C(29)  C(30)  112.3(2)  N(6)  C(30)  C(29)  112.9(3)  N(5)  C(31)  C(32)  114.8(2)  N(7)  C(32)  C(31)  116.5(3)  N(7)  C(32)  C(33)  121.5(3)  C(31)  C(32)  C(33)  121.8(3)  C(32). •  CC33)  C[34)  119.4(3)  C(33)  C(34)  C(35)  119.8(3)  C(34)  C:351  C(36)  117.5(3)  N(7)  C(36)  C(35) ,  123.6(3)  N(5)  C(37j  C(38)  111.9(2)  C(37)  C(38)  C(39)  118.3(2)  C(37j  C(38)  C(43)  123.2(3)  C(39)  C{38)  C(43)  118.4(3)  0(3)  C(39)  C(38)  116.4(3)  0(3)  C(39)  C(40)  121.6(3)  C(36)  C(39)  C(40)  120.0(3)  C(39)  C(40)  C(41)  120.0(3)  C(40)  C(41)  C(42)  120.8(3)  C{41)  C(42)  C(43)  119.1(3)  C(38)  C(43)  C(42)  121.4(3)  N(6)  C(44)  C(45)  115.6(2)  N(8)  C(45)  C(44)  117.9(3)  N(8)  C(45)  C(46)  122.5(3)  C(44)  C(45)  C(46)  119.5(3)  C(45)  C(46)  C(47)  119.2(4)  C(46)  C(47)  C(48)  116.9(4)  C(47)  C(48)  C(49)  118.9(3)  N(B)  C(49)  C(48)  122.3(3)  N(6)  C(50)  C(51)  112.0(2)  C(50)  C(51)  C(52)  118.2(3)  C(50)  C(51)  C(56)  122.1(3)  C(52)  C(51)  C(56)  119.7(3)  0(4)  C(52)  C(51)  119.7(3)  0(4)  C(52)  C(53)  121.0(3)  C{51)  C(52)  C(53)  119.1(3)  C(52)  C(53)  C(54)  119.9(3)  C(53)  C(54)  C<55)  121.5(3)  C(54)  C(55)  C(56)  118.5(3)  C(5i)  C(56)  C(55)  121.3(3)  - 137-  Appendices  Table A10. Bond Lengths (A) and Bond Angles (deg) for [Gd (Ll) (N03)][N03]»CH OH»3H 0. 2  2  3  2  atom  atom  distance  atom  atom  distance  atom  atom distance  atom  atom  distance  Gd(l)  Gd(2)  3.6362(3)  Gd(l)  0(1)  2.230(3)  N(8)  C(49) 1.336(5)  C(l)  C(2)  1.500(6)  Gd(l)  0(2)  2 409(3)  Gd(l)  0(3)  2.524(3)  C(3)  C(4)  1.494(6)  C(4)  C(5)  1.392(6)  Gd(l)  0(4)  2.377(3)  Gd(l)  N(l)  2.728(3)  0(5)C(6)  1.372(7)  C(6)  C(7)  1.393(7)  Gd(l)  N(2)  2.665(4)  Gd(l)  N(3)  2.501(3)  C(7)  C(8)  1.368(6)  C(9)  C(10) 1.501(6)  Gd(l)  N(4)  2.613(4):  Gd(2)  0(2)  2.336(3)  C(10)  C ( l l ) 1.414(6)  C(10)  C(15) 1 397(6)  Gd(2)  0(3)  2.361(3)  Gd(2)  0(4)  2.467(3)  C(U)  C(12) 1.400(6)  C(12)  C(13) 1.395(6)  Gd(2i 0:5:  2.481(3)  Gd(2)  0(6)  2.507(3)  C(13)  C(14) 1.385(7)  C(14)  C(15) 1.390(7)  Gd{2) N(5)  2.586(3)  Gd(2)  K(6)  2.697(4)  C O 6)  C,{17)  1.490(6)  C(17)  C(18) 1.374(6)  Gd(2) S-7) 2 654 4,  Gd(2)  N(8)  2.647(4)  C(18)  C(19) 1.379(7)  C(19)  C(20) 1.391(7)  1.327(5)  0(2)  C(24) 1.352(4)  C(20)  C(21) 1.392(7)  C(22)  C(23) 1.502(6)  0(4)  C(52) 1.378(5)  C(23)C(24)  1.403(6)  C(23)  C(28) 1 406(6)  i;|89(4);:;  0(6)  N(9)  C(24:  C(25) 1.399(6)  C(25)  C(26) 1.402(6)  S(10) 1.235(9)  C{26;  C(2;j 1.369(7)  C(27)  C(28) 1.373(7)  0(3)  C(39)  0('5)  1.280(4)  0(7.)  N S.  1.220(5)  0(6)  0(9i  N(io;  1.196(9)  0(10) N(10) 1.273(8)  C(29)  C(30) 1.468(7)  C(31)  C(32) 1.495(6)  •if!  C(57)  1.395(9)  K(l)  C(l)  1.487(6)  C(32)  C(33) 1.370(6)  C(33)  C(34) 1.383(6)  N(l)  C3  1 497(5.!  N(l)  C(9)  1.508(6)  G(34)  C(3o) 1.392(6)  C(35)  C(36) 1.371(7)  N(2)  C(2j'  1.495(5)  N(2)  C(,16) 1.491(5)  C(37)  C(36) 1.493(6)  C(38)  C(39) 1.410(5)  N(2)  C(22,  1.487(6)  N(3) C(4)  1.331(5)  C(38)  C(43) 1.398(6)  C(39)  C(40) 1.407(6)  1.353(6)  N(4) C(17) 1.358(6)  C(40)  C(41) 1.375(6)  C(41)  C(42) 1.384(6)  C(42)  C(43) 1.389(7)  C(44)  C(45) 1.500(6)  C(46) 1.375(7)  C(46)  C(47) 1.388(6)  C(48)  C{49) 1.362(7)  N(3) M4)  G(21)  1.358(6)  K(5)  C(29) 1.501(6)  N(5)  C(31)  1.479(6)  N(5) C(37) 1.504(6)  C{45)  N(6)  C(30j  1.499(6)  N(6) C(44) 1.478(6)  C(47)C(46)  N(6)  C(50)  1.501(6)  N(7) C(32) 1.347(5)  C(50)  C(51) 1.503(7)  C{51)  C(52) 1.408(6)  N(7)  C(36)  1.355(5)  N(8) C(45) 1.34bi5)  C(51)  C(56) 1.398.(6)  C{52)  C(S3) 1.380(6)  C(53)  C(54) 1.390(6)  G(t>4)  C(55) 1.389(6)  C(55)  C(56) 1.380(7)  - 138-  1.395(6)  Appendices  Table A10. Continued. atom'  atom  atom  angle  atom  atom  atom  angle  0(1)  Gd(l)  0(2)  142.16(11)  O(l)  Gd(l)  0(3)  85.07(10)  O(l).  Gd(l)  0(4)  123.91(10)  O(l)  Gd(l)  N(D  74.06(11)  O(l)  Gd(l)  N(2)  136.18(11)  O(l)  Gd(l)  N(3)  78.38(11)  0(1)  Gd(l)  N(4)  .65.25(12)  0(2)  Gd(l)  0(3)  69.37(9)  0(2)  Gd(l)  0(4)  70.59(9)  0(2)  Gd(l)  N(l)  116.16(10)  0(2)  Gd(l)  N(2)  75.81(11)  0(2)  Gd(l)  N(3)  74.79(11)  0(2)  Gd(l)  132.33(11)  0(3)  Gd(l)  0(4)  65.28(10)  0(3)  Gd'l)  150.48(10)  0(3)  Gd(l)  N(2)  13B.37(10)  Gd;i)  91.01(11)  0(3)  Gd(l)  N(4)  126.64(10)  Gd(l").  144.12(11)  0(4)  Gd(l)  N(2)  82.31(10)  143.11(11)  0(4)  Gd(l)  N(4)  77.73(10)  Gd(l)  66.91(11)  Nd)  Gd(l)  N(3)  64.81(11)  Gd(l)  72.99(10)  Gd(l)  N(3)  101.37(11)  N(2l  Gdfl)  65.25(11)  Gd(l)  N(4)  137.43(11)  0(2)  Gd!2)  0(3)  73.47(10)  0(2)  Gd(2)  0(4)  70.26(9)  0(2)  Gd(2j  l i i i l  126-32(9)  0(2)  Gd(2)  0(6)  75.10(10)  0(2.  Gd;2)  153 16(11)  0(2)  Gd(2)  N(6)  131.99(12)  0(2)  Gd(2)  N(7)  99.30(10)  0(2)  Gd(2)  N(8)  84.85(11)  0(3)  Gd(2)  0(4)  66.45(10)  0(3)  Gd(2)  0(5)  139.22(11)  0(3)  Gd(2)  0(6)  122.31(10)  0(3)  Gd(2)  N(5)  80.66(11)  0(3)  Gd(2)  N(6)  116.50(11)  0(3)  Gd(2)  N(7)  71.67(11)  0(3)  Gd(2)  N(8)  151.45(11)  0(4)  Gd(2)  0(5)  148.95(10)  0(4)  Gd(2)  0(6)  139.50(9)  0(4)  Gd(2)  N(5)  105.92(10)  0(4)  Gd(2)  N(6)  73.59(11)  0(4)  Gd(2)  N(7)  138 10(11)  0(4)  Gd(2)  K{8)  89 07(11)  0(5)  Gd(2)  0(6)  51.B8(9)  O(S)  Gd(2)  N(5)  70.92(11)  0(5)  Gd(2)  N(6)  76.99(11)  0(5)  Gd(2)  N(7)  70.09(11)  0(5)  Gd(2)  N(8)  68.99(12)  0(6)  Gd(2)  N(5)  114.44(11)  0(6)  Gd(2)  N(6)  118.60(11)  0(6)  Gd(2)  N(7)  , 67.31(11)  0(6)  Gd(2)  N(8)  67.26(11)  N(5)  Gd(2)  N(6)  67.53(12)  N(5)  Gd(2)  N(7)  65.10(11)  N(5)  Gd(2j  N(8)  121.95(11)  N(6)  Gd(2)  N(7)  128.70(11)  N(6)  Gd(2j  N(S)  63 67(11)  N(7)  Gd(2)  N(8)  13144(12)  Gd(l) ••  Nd)  N(3)  -139-  Appendices  Table A10. Continued. atom  Gd;2)  atom  atom  angle  atom Gd(l)  0(2)  Gd(2)  100.03(10)  atom  atom  angle  O(l)  C(ll)  133.5(2)  0(2)  C(24.)  118.3(3)  Gd(2)  0(2)  C(24)  141.5(3)  0(3;  Gd(2)  96.13(10)  Gd(l)  0(3)  C(39)  135.2(3)  o;3,  C(39)  128.3(3)  Gd(l)  0(4)  Gd(2)  97.28(10)  116.1(3)  Gd(2)  0(4)  C(52)  117.1(3)  96 4(2)  Gd(2)  0(6)  N(9)  95.4(2)  GdU) Ovo.  N(9)  GdtJVd!:!;:  N(l')  SI )''':  110.9(3)  Gd(l)  N(D  C(3)  110.7(3)  Gd(lj  N(D  C(9)  111.1(2)  C(l)  NO)  C(3)  108.6(3)  C(i)  N(,l)  106.6(4)  C(3)  N(l)  C(9)  108.6(4)  Gd(l)  N(2).  C(2)  113.5(3)  Gd(l)  N(2)  C(16)  104.8(2)  Gd(l)  N(2)  C(22)  111 8(3)  C(2)  N(2)  C(16)  110.2(4)  C(2)  N(2)  C(22)  109.6(3}  C(16)  N(2)  C(22)  106.6(4)  Gd(l)  N(3)  C(4)  123.3(3)  Gd(l)  N(3)  C(B)  115.5(3)  C(4)  N(3)  C(8)  118-5(4)  Gd(l)  N(4)  C(17)  117.8(3)  Gd(l)  N(4)  C(21)  124.3(3)  C(17)  N(4)  C(21)  117.1(4)  1  Gd(2)  N(S)  C(29)  110.7(3)  Gd(2)  N(5)  C(31)  115.6(2)  Gd(2)  N(5)  C(37)  104.8(2)  C(29)  N(5)  C(31)  107.0(4)  C(29)  N(3)  C(37)  109.6(3)  C(31)  N(S)  C(37)  109.0(4)  Gd(2)  N(6)  C(30)  111.7(3)  Gd(2)  N(6)  C(44)  107.0(3)  Gd(2)  N(6)  C(50)  113.0(3)  C(30)  N(6)  C(44)  107.0(4)  C(30)  N(6J  C(50)  110-2(4)  C(44)  N(6)  C(50)  107.7(4)  Gd(2)  N(7)  C(32)  118.9(3)  Gd(2)  N(7)  C(36)  122.6(3)  C<32,  N(7)'  C(36)  116 4(4)  Gd(2)  N(8)  C(45)  117.9(3)  Gd(2)  N(6)  123 4(3)  C(45)  N(8)  C(49)  118.0(4)  0(5)  N(9)  0(6)  116.3(4)  0(5)  N(9)  0(7)  121.3(4)  0(6,  N(9..  0(7}  122 4(4)  O(S)  1S(10)  0(9)  1236(10)  0(6)  N(10;  O{10)  117.3(10)  0(9)  N(10)  0(10)  119.2(10)  Ml)  C{1)  112.0(4)  N(2)  C(2)  C(l)  115.7(4) 116.5(4)  C(3)  C(4)  112.1(3)  N(3)  C(4)  C(3)  C(4)  C(5)  121.8(5)  C(3)  C(4)'  C(5)  118.8(4)  C(5)  C(6)  C(7)  120 1(5)  C(5)  '  121.5(4)  C(6)  C;T)  C(8)  117.4(5)  N(3)  C<8)  C(7)  123.4(4)  N(D  C(9)  C(10)  112.2(4)  C(9)  C(10)  C(ll)  119.9(4)  C(9)  C(10)  C(15)  120.4(4)  C(ll)  COO)  C(15)  119.7(5)  - 140-  Appendices  Table A10. Continued. atom  atom  atom  angle  atom  atom  atom  angle  O(l)  C(ll)  C(10)  120.2(4)  O(l)  C(ll)  C(12)  121.3(4)  C(10)  C(ll)  C(12)  118.4(4)  C(ll)  C(12)  C(13)  121.1(5)  C(12)  C(13)  C(14)  120.1(5)  C(13)  C(14)  C(15)  119.7(5)  C(10)  C(15)  C(14)  120.9(5)  N(2)  C(16)  C(17)  112.9(4)  N(4)  C(17)  C(16)  115.1(4)  N(4)  C(17)  C{18)  123.2(4)  C(16;  C(17)  C(18)  121.7(4)  C(17)  C(18)  C(19)  119.3(5)  C(18)  C(19)  C(20)  119.2(5)  C(19)  C(20)  C(21)  118.5(5)  N(4)  C(21)  C(20)  122.8(5)  N(2)  C(22)  C(23)  114.1(4)  C(22)  C(23)  C(24)  118.6(4)  C(22)  C(23)  C(28)  121.5(4)  C(24)  C(23)  C(28)  119.7(4)  0(2)  C(24)  C(23)  1197(4)  0(2)  C(24)  C(25)  121.2(4)  C(23)  C(24)  C(25)  119-1(4)  C(24)  C(25)  C(26)  119.8(4)  C{25)  C(26)  C(27)  121.0(5)  C(26)  C;27)  C(26)  119.2(4)  C(23)  C(28)  C(27)  121.2(5)  N(5)  C(29,  C(30)  112.9(4)  N(6)  C(30)  C(29)  112.7(4)  C(31)  C(32)  114.9(4)  N(7)  C(32)  C(31)  115.7(4)  C(32;  C(33)  122.8(4)  C(31)  C(32)  C(33)  121.3(4)  C(32)  C(33)  C(34)  120.6(4)  C(33)  C(34)  C(35)  117.0(5)  :c|3|j||  C(35)  C(36)  119.4(4)  N(7)  C(36)  C(35)  123.6(4)  N(5)  C!37.  C(3S)  114.0(4)  C(37)  C(38)  C(39)  122 7(4)  COT)  Ci3S,  C(-43)  118.5(4)  C(39)  C(38)  C(43)  118.8(4)  o;3;  C(39)  IIPlP'::?:  121.0(4)  0(3)  C(39).  C(40)  120.6(4)  C(39)  C{40)  118.3(4)  C(39)  C(40)  C(41)  121.2(4)  C(40)  C(41)  C(42)  121.2(5)  C(41)  C(42)  C(43)  116.1(5)  C(38)  C(43)  C(42)  122.3(4)  N(6)  C(44)  C(45)  114.1(4)  N(8)  C(45)  C(44)  117.7(4)  N(8).  C(4S)  C(46)  122.1(4)  C(44)  C(45)  C(46)  119.9(4)  C(45)  C(46)  C(47)  119.2(5)  C(46)  C(47)  C(48)  118.7(5)  C(47)  C(48)  C(49)  1181(4)  N(8)  C{49)  C(48)  123.9(4)  N(6)  C(50)  C(51)  109.9(4)  C(50)  C(51)  C(52)  119.1(4)  C(50)  C(51)  C(56)  121.6(4)  C(52)  C(51)  C(56)  118.7(5)  0(4)  C(52)  C(51)  118.2(4)  0(4)  C(52)  C(53)  122.1(4)  C{51)  C(52)  C(53)  119.5(4) .  C(52)  C(53)  C(54)  120.4(4)  C(53)  C(54)  C(55)  121.1(5)  C(54)  C(55)  C(56)  118.2(4)  C(51)  C(56)  C(55)  122.0(5)  1  - 141 -  Appendices  Table All. Bond Lengths (A) and Bond Angles (deg) for [Gd (L3) (CH3COO)4(CH OH)] C104«5CH3OH 3  atom  atom  2  3  atom  distance  atom  distance  ;;Gdt|  0(1)  2.424(5)  Gd(l)  Gd(l)  0(5)  2.336(5)  Gd(l)  0(7)  2.503(6)  Gd(l)  0(8)  2.487(5)  Gd(l)  NO)  2.643(6)  Gd(l)  N(2)  2.659(7)  Gd(l)  N(3)  2 577(7)  2 593(6)  Gd(2)  0(1)  2.350(4)  Gd(l)  0(2)  2.450(5)  atom  atom  distance  atom  atom  distance  C(29)  1.476(9)  N(5)  C(31)  1.464(9)  1 475(9)  N(6)  C(30)  1 481(9)  1.474(9)  N(6)  C(50)  1.505(10)  N{7)  C(36)  1.313(9)  C(49)  1.368(9)  - N : ( 5 ) | !|(37J;; :  :  :  N(6)  -:^(7)f ' '$0. ;  N(8)  0:21  2.342(5)  Gd(2)  0(3)  2.413(5)  Gd;2)  04  2.371(5)  Gd(2)  0(6)  2.347(5)  Gd?2..  o & 1|1P|5|.{|  Gd(2)  0(10)  2.441(5)  Gdi2.  o;nj  Gd(3)  0(3)  2.364(5)  Gdi3;  04  2-447(5)  Gd(3)  0(9)  2 432(5)  Gci3-  0(12;  2 471(5)  Gd(3)  0(13)  2.500(5)  Gd.3;  N,5;  2:727(0)  Gd 3  N.'T;  ;§lf§6J;.;:::»|  •BY;^i cm-' Br!3  C 12  1,902(7]  0  1.424(9)  14  0(1C)  1 474(9)  f'  :  ;:j G|(3); ;' N(6) :  :  :'-eoi::lMM  Gd(3)  N(8)  2.553(6)  Br(2)  C(27)  1.876(8)  Br(4)  C(55)  1.891(8)  0(15)  1.431(9)  0(17)  1.417(9)  |!;*ci|i|-: Cl(l)  :  C(6)  2.598(6)  Mill  C(ll)  1.342(8)  0(2)  C(24)  1.329(8)  0(3)  C(39)  1.327(8)  0(4)  C(52)  1.367(8)  0(5)  C(57)  1.217(9)  0(6)  C(57)  1 283(10)  C(59)  1.246(9)  0(8)  C(59)  1.275(11)  0(9)  C(61)  1.288(9)  0(10)  C(61)  1.260(9)  0(11)  C(63)  1.451(13)  0(12)  C(64)  1.248(8)  0(13)  C(64;  1.328(10)  0(18)  C(66)  1.343(14)  0(19)  C(67)  1.298(13)  0(20)  £(66)  1.456(10)  0(21)  C(69)  1.53(2)  0(22)  C(70)  1.45(2)  N(D  C(l)  1.472(10)  N(l)  C(3)  1513(11)  C(9)  1.480(10)  N(2)  NO)  C(2)  1.508(9)  N(2)  C(16)  1.490(10)  N(2)  C(22)  1.496(10)  N(3)  C(4)  1,354(11)  N(3)  C(8)  1.322(11)  C(17)  1.338(10)  N(4)  C(21)  N(4).  1.347(10)  ; :  C(7)  1.502(12)  C(3)  C(4)  1.500(14)  1 343(12)  C(5)  C(6)  1.42(2)  1.39(2)  C(7)  C(8)  1.330(13)  1.463(10)  COO)  C(ll)  1 434(10)  C(10)  C(15)  1 430(9)  C(I1)  C(12)  1.376(10)  C(12)  C(13)  1.403(10)  C(13)  C(14)  1.394(11)  C(14)  C(15)  1.394(11)  C(16)  C(17)  1.512(11)  C(17)  COS)  1.368(11)  C(18)  C(19)  1.384(12)  C(19)  C(20)  1.383(13)  C(20)  C(21)  1.361(12)  C(22)  C(23)  1.494(10)  C(23)  C(24)  1 405(10)  C(23)  C(28)  1.380(10)  C(24)  C(25)  1.393(10)  C(25)  C(26)  1.360(10)  C(26)  C(27)  1.415(12)  C(27)  C(28)  1 404(11)  C(29)  C(30)  1.520(10)  C(31)  C(32)  1.487(10)  C(32)  C(33)  1.388(10)  C(33)  C(34)  1.419(11)  C(34)  C(35)  1.371(11)  C(35)  C(36)  1.397(12)  C(37)  C(38)  ,1.485(10)  C(38) C(39)  1.422(9)  C(38)  C(43)  1.402(10)  C(39)  C(40)  1.400(10)  C(40)  C(41)  1.378(10)  C(41)  C(42)  1.368(10)  C(42)  C(43)  1 427(10)  C(45)  1 568(11)  C(45)  C(46)  .1.374(11)  C(46)  C'47,  1.324(13)  C(47)  C(48)  1.382(14)  C(4S)  C(49)  1 35101)  C(50)  C(51)  1.510(11)  1 394(10)  C(51)  C(56)  1.366(10)  C'53j  1.441(10)  C(53)  C(54)  1.374(10)  C(54) C(55)  1.395(11)  C(55)  C(56)  1.415(11)  c;5*.  1.509(11)  C(59)  C(60)  1.493(12)  C(61) C(62) , 1.474(10)  C(64)  C(65)  .1.509(12)  :|:JG|M!!  C(51)  itiiiii  - 142-  :  1.304(10)  :  Gd{2]  1.385(9)  Appendices  Table A l l . Continued. atom  atom  atom  angle  atom  atom  atom  angle  O(l)  Gd(l)  0(2)  64.39(15)  0(1)  Gd(l)  0(5)  81.5(2)  O(l)  Gdd)  0(7)  138 2(2)  O(l)  Gd(l)  0(8)  141.4(2)  O(l)  Gd(l)  , Nd)  74.3(2)  0(1)  Gd(l)  N(2)  101.9(2)  0(1)  Gd{l)  ' NO)  77.6(2)  O(l)  Gd(l)  N(4)  144.6(2)  0(2)  Gd(l)  0(5)  75.1(2)  0(2)  Gd(l)  0(7)  131.2(2)  0(2)  Gd(l)  0(8)  145 7(2)  0(2)  Gd(l)  N(l)  114.7(2)  0(2)  Grf'l)  73.1(2)  0(2)  Gd(l)  N(3)  138.6(2)  0(2)  Gd'l)  80.2(2)  0(5)  Gd(l)  0(7)  69.9(2)  0(5)  Gd(l)  121.9(2)  0(5)  Gd(l)  N(D  145.0(2)  O{o;  Gdll)  142.4(2)  0(5)  Gd(l)  N(3)  64.0(2)  0(5:  Gd-1 •  90.9(2)  0(7)  Gd(l)  0(8)  52.1(2)  113.5(2)  0(7)  Gd(l)  N(2)  119.4(2)  O(S)  ||p(pl?|  ' Gd(lJ Gd l i  N(3)  69 6(2)  0(7)  Gd(l)  N(4)  67:7(2)  Gd(l)'  Nd)  69.9(2)  0(8)  Gd(l)  N(2)  78.1(2)  o;?>  Gd.'l)  N(3)  75.4(2)  0(8)  Gd(l)  N(4)  70.8(2)  N(U  Odd.  6B 7(2)  Nd)  Gd(l)  N(3)  66.5(2)  N(D  Gdd>  N(4)  123 3(2)  N(2)  Gd(l)  N(3)  133.5(2)  N(2)  Gd(l)  N(4)  64 5(2)  N(3)  Gd(l)  N(4)  136.2(2)  O(l)  Gd(2)  0(2)  £7.2(2)  O(l)  Gd(2)  0(3)  81.4(2)  O(J)  Gd(2)  0(4)  99.4(2)  O(l)  Gd(2)  0(6)  78.8(2)  O(l)  Gd(2)  0(9)  144.7(2)  O(l)  Gd(2)  0(10)  126.7(2)  O(l)  Gd(2)  O(ll)  146.0(2)  0(2)  Gd(2)  0(3)  113.7(2)  0(2)  Gd(2)  0(4)  164.8(2)  0(2)  Gd{2)  0(6)  83.6(2)  0(2)  Gd(2)  0(9)  126.7(2)  0(2)  Gd(2)  0(10)  76.5(2)  0(2)  Gd(2)  0(11)  99.7(2)  0(3)  Gd(2)  0(4)  69.3(2)  0(3)  Gd(2)  0(6)  145.9(2)  0(3)  Gd(2)  0(9)  63.3(2)  0(3)  Gd(2)  0(10)  79.0(2)  0(3)  Gd(2)  O(ll)  129.8(2)  0(4)  Gd(2)  0(6)  86.8(2)  0(4)  Gd(2)  0(9)  68.3(2)  0(4)  Gd(2).  0(10)  118.4(2)  0(4)  Gd(2)  O(U)  88.1(2)  0(6)  Gd(2)  0(9)  130.6(2)  0(6)  Gd(2)  0(10)  135.0(2)  0(6)  Gd!2.  0(11)  70.6(2)  0(9)  Gd(2)  0(10)  50.2(2)  0(9)  Gd(2]  O(ll)  66.8(2)  0(10)  Gd(2)  O(ll)  73 5(2)  0(3)  Gd(3;  0(4)  68.9(2)  0(3)  Gd(3)  0(9)  69.0(2)  - 143 -  Appendices  Table A l l . Continued. atom  atom  atom  angle  atom  atom  atom  angle  0. 3  Gd(3,.  0(12)  145.4(2)  0(3)  Gd(3)  0(13)  126.5(2)  0(3  Gd;3 ,  N(5)  72.0(2)  0(3)  Gd(3)  N(6)  117.7(2)  0(3)  Gd(3;  74.6(2)  0(3)  Gd(3)  N(8)  138.6(2)  -  -  .0(4),  Gd(3)  0(9)  72.5(2)  0(4)  Gd(3)  6(12)  142.7(2)  Gc 3  Od3)  129.2(2)  0(4)  Gd(3)  N(5)  104.3(2)  77.8(2)  0(4)  Gd(3)  N(7)  143.3(2)  Gd(3) Gd:3:  N(8)  72.2(2)  0(9)  Gd(3)  0(12)  124.7(2)  OO;  Gd:3;  Od.3)  71.6(2)  0(9)  Gd(3)  N(5)  139.1(2)  0(9)  Gd;3)  N(6)  144.3(2)  0(9)  Gd(3)  N(7)  91.7(2)  0(9)  Gd(3)  N(8)  86.6(2)  0(12)  Gd(3)  0(13)  53.1(2)  0(12)  Gd(3)  N(5)  83.2(2)  0(12)  Gd(3)  N(6)  71.5(2)  0(12)  Gd(3)  N(7)  73.5(2)  0(12)  Gd(3)  N(8)  76.0(2)  0(13)  Gd(3)  N(5)  126.3(2)  0(13)  Gd(3)  N(6)  115.5(2)  0(13)  Gd(3)  N(7)  71.9(2)  0(13)  Gd(3)  N(8)  70.9(2)  Gd(3)  N(6)  67.3(2)  N(5)  Gd(3)  N(7)  66.3(2)  N(5)  Gd(3)  N(8)  132.3(2)  N(6)  Gd(3)  N(7)  123.9(2)  N(6)  Gd(3)  N(8)  65.5(2)  N(7)  Gd(3)  N(8)  141.3(2)  0(14)  OO)  0(15)  110.0(7)  0(14)  Cl(l)  0{16)  109.1(7)  0(14)  Cld)  0(17)  108.3(5)  0(15)  Cl(l)  0(16)  106.9(6)  0(13)  Cl(l)  0(17)  112.0(8)  0(16)  Cl(l)  0(17)  110.5(6)  Gd(l)  Od)  Gd(2)  111.9(2)  Gd(l)  O(l)  C(ll)  122.8(4)  Gd(2)  Oil)  C(ll)  123 7(4)  Gd(l)  0(2)  Gd(2)  111.3(2)  Gd.l:  0,2;  C(24)  117.6(4)  Gd(2)  0(2)  C(24)  130.5(4)  Gd,2.  0(3'  102.5(2)  Gd(2)  0(3)  C(39)  125.4(4)  Gd;3  0.3  C(39)  131 2(4}  Gd(2)  0(4)  Gd(3)  101.3(2)  Gd;a  04)  C(52)  133.5(5)  Gd(3)  0(4)  C(52)  124.2(4)  Gdfi;  Ola)  C(57j  140.7(6)  Gd(2)  0(6)  C(57)  132.6(5)  Gdd),  o:?;  C(59)  93.4(5)  Gd(l)  0(8)  C(59)  93.5(5)  92.14(15)  Gd(2)  0(9)  C(61)  87.3(4)  Gd(2)  ||pd(|)|ll:  '  Gd(3j  0;9-,  C(61)  139 4(5)  Gd(2)  0(10)  C(61)  101.9(5)  Cd(2,  O d D  C(63)  137.4(7)  Gd(3)  0(12)  C(64)  95.4(5)  Gd(3)  0(13.  C(64)  92.0(4)  Gd(l)  N(l)  C(l)  107.5(4)  Gd(l)  Nd)  •C(3)  109.1(5)  Gd(l)  N(D  C(9)  112.9(4)  - 144-  Appendices  Table A l l . Continued. atom  atom  atom  angle  atom  atom  atom  angle  C(l)  N(l)  C(3)  109.0(6)  C(l)  N(l)  C(9)  109.1(7)  C(3)  N(l)  C(9)  109.2(6)  Gd(l)  N(2)  C(2)  110.8(5)  Gd(l)  N(2)  C(16)  106.7(5)  Gd(l)  N(2)  C(22)  115.8(4)  C(2)  N(2)  C(16)  107.4(6)  C(2)  N(2)  C(22)  106.4(7)  C(16)  N(2)  C(22)  109.3(6)  Gd(l)  N(3)  C(4)  119.3(6)  Gd(l) Gd(l)  N(3)  C(8)  120.9(6)  C(4)  N(3)  C(8)  119 6(8)  N(4J  C(17)  118.5(5)  Gd(l)  N(4)  C(21)  123.5(6)  C(17)  N(4)  C(21)  117.6(7)  Gd(3)  N(5)  C(29)  111.3(4)  Gd(3)  N(5)  C(31)  106.0(4)  Gd(3) .  N(5)  C(37)  114.0(4)  C(29)  N(5)  C(31)  108.3(6)  C(29)  N(5)  C(37)  106.3(5)  C(31)  N(5)  C(37)  111-0(6)  Gd(3)  N(6)  C(30)  108.5(4)  Gd(3)  N<6)  C{44)  112.5(4)  Gd(3)  N(6)  C(50)  109.7(4)  \,C(3f7): ||  N;e.  C(44)  107.1(6)  C(30)  N(6)  C(50)  106.3(5)  C(44)  Nf6)  C(50)  110.7(6)  Gd(3)  N(7)  C(32)  118.5(4)  Gd 3.  N(7)  C(3C)  122.7(5)  C(32)  N(7)  C(36)  118.5(7)  Gd(3:  N(S)  122.3(5)  Gd(3)  N(8)  C(49)  120.9(5)  115 9(7)  Nd)  CO)  C(2)  112.8(6)  N(l)  C(3)  C(4)  113 7(6)  C(4)  C(5)  121.2(10)  :  v  M5) N(2>  Hill?* S  C(2)  C(l)  112 4(7)  CU,  C(3)  117.4(7)  C(3;  C{4)'.  C(5)  C!C  N(3)  Illi^S  121.1(10)  C(4)' '  C(5)  C(6)  116.5(11)  C(T;  122.9(10)  C(6)  C(7)  C(8)  113.9(11)  C(S)  C(7)  126 0(10)  NO)  C(9)  C(10)  113.8(7)  C(9;  C(10)  Cdi)  119.0(6)  C(9)  C(10)  C(15)  121.1(7)  C(ll,  C(10)  C{15)  119.8(7)  0(1)  C(ll)  C(10)  117 4(6)  O(l)  C(ll)  C(12)  123.2(7)  C(10)  C(ll)  C(12)  119.5(6)  C(ll)  C(12)  C(13)  121 6(7)  C(12)  C(13)  C(14)  118.5(7)  Br(l)  C(14)  C(13)  119.3(6)  Br(l)  C(I4)  C(15)  117.7(6)  C(13)  C(14)  C(15)  122.9(7)  C(10)  C(15)  C(14)  117.7(7)  N(2)  C(16)  C(17)  113.4(6)  N(4)  C(17)  C(16)  117.2(7)  N(4)  C(17)  C(18)  122.6(8)  C(16)  C(17)  C(18)  120.1(7)  C(17)  C(18)  C(19)  119.6(8)  C(18)  C(19)  C(20)  117.8(8)  C(19)  C(2Q)  C(21)  119.5(8)  N(4)  C(21)  C(20)  122 9(8)  N(2)  C(22)  C(23)  114.0(7)  C(22)  C(23)  C(24)  118 2(7)  C(22;  C(23)  C(28)  120.4(7)  C(24)  C(23)  C(28)  121.3(7)  - 145-  ,  Appendices  Table A l l .  Continued.  atom  atom  atom  angle  atom  atom  atom  angle  0(2)  C(24)  C(23)  120.1(6)  0(2)  C(24)  C(25)  121.8(7)  C(23)  C(24)  C(25)  118.0(7)  C(24)  C{25)  C(26)  121.5(7)  C(25)  Cf2f.,:  C(27)  120.8(7)  Br(2)  C(27)  C(26)  121.0(6)  Br(2)  C(27,  lPC-(28^:so;  120.6(7)  C(26)  C(27)  C(28)  118.3(7)  C(23)  C(2S)  C(27)  120.0(8)  N(5)  C(29)  C(30)  113.4(5)  C(3C;  C(29)  111.6(6)  N(5)  C(31)  C(32)  115.1(6)  C(32j  C(3])  117.2(6)  N(7)  C(32)  C(33)  120.1(7)  C(31)  C(32;  C(33)  122.6(7)  C(32)  C(33)  C(34)  120.2(7)  C(33)  C(34:  C(35)  118.0(7)  C(34)  C(35)  C(36)  118.7(7)  N(7)  Ci3G;  C(35)  124.2(7)  N(5)  C(37)  C(38)  116 3(6)  C(37)  C(3S)  C(39)  119.0(6)  C(37)  C(38)  C(43)  120.6(6)  C(39)  C(35)  C(43)  120.0(7)  0(3)  C(39)  C(36)  118.9(6)  0(3)  C(39)  C(40)  122.3(6)  C(38)  C(39)  C(40)  118.7(6)  C(39)  C(40)  C(41)  121.1(7)  C(40)  C(41)  C(42)  120.0(7)  Br(3)  C(42)  C(41)  120.1(6)  Br(3)  C(42)  C(43)  118.5(6)  C(41)  C(42)  C(43)  121.4(7)  C(38)  C(43)  C(42)  118.1(7)  N(6)  C(44)  C(45)  111.5(6)  N(8)  C(45)  C(44)  115.2(7)  N(8)  C(45)  C(46)  123.5(8)  C(44)  C(45)  C(46)  121.2(8)  C(45)  C(46)  C(47)  119.9(9)  C(46)  C(47)  C(48)  119.1(8)  C(48)  C(49)  118.1(8)  N(8)  C(49)  C(4B)  123.4(8) 118:8(7)  C(47)  :  C(50)  C(51)  113 7(6)  C(50)  C(51)  C(52)  C(50;  C(51)  C(56)  119:5(7)  C(52)  C(51)  C(56)  121.6(7)  0(4)  C(52)  C(51)  122.8(7)  0(4)  C(52)  C(53)  118.1(7)  C(5i;  C(52)  C(53)  119.0(7)  C(52)  C(53)  C(54)  118.8(7)  C(53.  C(54)  C(55)  121.2(8)  Br(4)  C(55)  C(54)  121.2(6)  Br(4)  C(55)  C(56)  119.0(6)  C(54)  C(55)  C(56)  119.8(7)  C(5C;  C(55)  119.4(7)  0(5)  C(57)  0(6)  126 7(7)  • C(57)  C(58)  117.3(8)  0(6)  C(57)  C(58)  115.9(7)  120.7(8)  0(7)  C(59)  C(60)  119.7(9)  N(6)  1  0(7)  C 59;  0(6;  O *.  Ci59  lIlGlob:);"' ;'  119.6(8)  0(9)  C(61)  0(10)  120.5(7)  0(9  CIG1)  C(G2)  120.3(6)  0(10)  C(61)  C(62)  119.1(7)  0(12.  C\G4'  0(13)  119 1(7)  0(12)  C(64)  C(65)  121.9(9)  0(13;  CiG-J.  C(6J)  M9.0(8)  v  1  - 146-  Appendices  Table A12. Bond Lengths (A) and Bond Angles (deg) for [Sm (L 1 ) (CH3COO) (N03)2(CH OH)] N0 «CH OH«3.65H 0. 3  ;  2  2  3  3  3  2  atom  atom  distance  atom  atom distance  atom  atom  distance  atom  atom  distance  Sm(l)  OI)  2.385(4)  Sm(l)  0(2)  2.406(3)  C(l)  C(2)  1.515(8)  C(3)  C(4)  1.522(7)  Sm(l)  O(S)  2.361(4)  : Sm(l)  0(7)  2.580(4)  ,C(4)  C(5)  1.400(8)  C(5)  C(6)  1.355(8)  Sm{l)  O(S)  2.569(4)  Szn(l)  N(l)  2 697(4)  C(6)  C(7)  1 375(9)  C(7)  C(8)  1.437(8)  C(10)  1.511(7)  C(10)  C(ll)  1.404(7)  Sm(l)  Mil  2.626(4)  Sm(l)  N(3)  2.585(5)  Sm(l)  N(4)  2.540(5)  Sm(2)  O(l)  2.365(4)  C(10)  C(15)  1.366(7)  C(U)'  C(12)  1.394(7)  Sm(2)  0(2,  2.377(4)  Sm(2)  0(3)  2.377(4)  C(12)  C(13)  1.394(8)  C(13)  C(14)  1.377(8)  2.403(4)  Sm(2)  0(6)  2.337(4)  C(14)  C(15)  1.401(8)  C(16)  C(17)  1.525(8)  2.469(4)  Sm(2)  0(12) 2.489(4)  C(16)  1.365(8)  C(16)  C(19)  1.364(8)  2.353(4)  Sm(3)  0(4)  Sm;(2)*; 0<4, o.io-  'Sm|3|;  0,3;  Sm(3;  O(ll)  Sm(3.. • f i l l  2.411(4)  C(19)  C(20)  1.419(8)  C(20)  C(21)  1 370(6)  [2lS4t4);f;r3 I Sm(3] 0(13) 2 525(4)  C(22)  C(23)  1 514(6)  C(23)  C(24)  1.410(7)  2.543(4)  Sm(3)  N(5)  2.715(4)  C(23)  C(28)  1.407(7)  C(24)  C(25)  1 380(7)  Srr.(3>  N(C)  2.609(4)  Sm(3)  N(7)  2.616(4)  C(25)  C(26)  1.382(7)  C(26)  C(27)  1.390(8)  Sm.'3;  N(6;  2.552(4)  0(1)  C(ll)  1.375(6)  C(27)  C(28)  1.366(8)  C(29)  C(30)  1.522(8)  0(3)  C(39)  1.349(5)  C(31)  C(32)  1.506(7)  C(32)  C(33)  1-373(7)  C(24)  Il57(|).;;::f  O 4)  C(52),  1.365(6)  0(5)  SI  1.239(6)  C(33)  C(34)  1.385(8)  C(34) C(35)  1.366(8)  0(C)  C(57)  1 270(6)  0(7)  N(9)  1.263(6)  C(35)  C(36)  1.390(7)  C(37)  C(38)  1.510(7)  C(38)  C(39)  1.402(7)  C(3S)  C(43)  1.405(7)  C(39)  C(40)  1.390(7)  C(40)  C(41)  1.392(7)  C(41)  C(42)  1.348(8)  C(42)  C(43)  1.407(8)  C(44)  C(45)  1 529(8)  C(45)  C(46)  1.399(7)  C(46)  C(47)  1.385(9)  C(47)  C(48)  1.341(9)  C(48)  C(49)  1.377(8)  C(50)  C(51)  1.506(8)  C(51) C(56)  1.404(7)  v  0(6)  N(9j  1.281(6)  0(9)  N(9)  1.258(7) .  !:ojip|:  C;59;  1.250(7)  O(ll)  C(59)  1.280(6)  0(12)  C(61)  1.406(7)  0(13) N(10)  1.283(6)  0(14)  M10)  1.275(6)  0(15) N(10)  1.244(6)  0(16)  Ndl)  1.209(9)  0(17) N ( l l )  1.236(9)  0(18)  N(ll)  1.224(10)  0(19) C(62)  1.375(8)  N(l)  C(l)  1.498(6)  N(l)  C(3)  1.487(7)  C(51)  C(52) • 1.387(8)  N(l)  C[9)  1.500(7)  N(2)  C(2)  1.474(7)  C(52)  C(53)  1.417(6)  C(53)  C(54)  1 404(8)  N(2)  C(16)  1.482(7;  N(2)  C(22)  C(55)  1.328(9)  C(55)  C(56)  1 352(9)  C(58)  1 505(7)  C(59)  C(60)  1.497(8)  1.490(7)  N(3)  C(4)  1.347(7)  N(3)  C(8)  'N(4)  C(17)  1.338(7)  N(4)  C(21) 1.357(7)  N(5)  C(29)  1.484(6)  N(5)  C(31)  1.469(7)  N(5)  C(37)  1.495(7)  N(6)  C(30)  1.517(7)  N(6)  C(44)  1.454(7)  N(6)  C(50) 1.483(7)  N(7)  Ci32j  1.337(7)  N(7)  C(36)  1.345(6)  N(8)  C(4V,  1.347(7)  N(8)  C(49)  1.336(7)  C(57)  1.336(7)  -147-  Appendices  Table A 1 2 . Continued. atom : i  atom  atom  angle  atom  atom  atom  angle  O(l)  Sm(l)  0(2)  6560(12)  O(l)  Sm(l)  0(5)  78.75(13)  O(l)  Sm(l)  0(7)  137.51(12)  'O(l)  Sm(l)  0(8)  148.89(13)  O(l)  Sm(l)  Nd)  73.69(13)  O(l)  Sm(-1)  N(2)  111.07(13)  O(l)  Sm(l)  N(3)  83.69(14)  oo)  Sm(l)  N(4)  136.92(13)  0(2)  Sm(l)  0(5) •  86.42(12)  0(2)  Sm(l)  0(7)  131.59(12)  0(2)  Sm(l)  0(8)  138.25(13)  0(2)  Sm(l)  N{1)  108.61(13)  6(2)  Sm(l):  N(2)  75 71(13)  0(2)  Sm(l)  N(3)  148.74(14)  0(2)  Sm(l)  N(4)  72-57(13)  0(5)  Sm(l)  0(7)  66.32(13)  Sm(l)  0(8)  115.98(13)  0(5)  Sm(l)  N(l)  138.75(14)  152.73(14)  0(5)  Sm(l)  N(3)  81.78(14)  .••®t5.)M;: :  ill?? s i  0(5)  Sm(l)  0(5)  Sm(l)  N(4)  89.11(14)  0(7)  Sm(l)  0(8)  49.84(12)  Sm(l)  Nd)  118.36(13)  0(7)  Sm(l)  N(2)  111.04(14)  Smd;  68 55(14)  0(7)  Sm(l)  N(4)  68.03(13)  Sm(l)  78.29(14)  0(8)  Sm(l)  N(2)  69.12(13)  :;;:;:!  O(S)  '  |l|m|i| ||  N(3)  72 41(15)  0(8)  Sm(l)  N(4)  73.08(14)  Smd;  N(2)  67.71(14)  N(D  Sm(l)  N(3)  65.37(14)  NO)  Smd)  N(4;  131.75(14)  N(2)  Sm(l)  N(3)  123.66(14)  N(2)  Sm(l)  N(4)  66.11(14)  N(3)  Sm.(l)  N(4)  135.63(15)  Od)  Sm(2)  0(2)  66.37(12)  O(l)  Sm(2)  0(3)  80.07(12)  od)  Sm(2)  0(4)  101.75(12)  oo)  Sm(2)  0(6)  76.90(12)  Od)  Sm(2)  0(10)  128.08(12)  0(1)  Sm(2)  0(12)  139.40(13)  0(2)  Sm(2)  0(3)  113.15(12)  0(2)  Sm(2)  0(4)  166.43(12)  0(2)  Sm(2)  0(6)  87.25(13)  0(2)  Sm(2)  0(10)  79.22(13)  0(2)  Sm(2)  0(12)  92.96(13)  0(3)  Sm(2)  0(4)  69.14(11)  0(3)  Sm(2j  0(6)  139.48(13)  0(3)  Sm(2)  0(10)  79.29(13)  0(3)  Sm(2)  0(12)  140.24(13)  0(4)  Sm(2)  0(6)  83.48(13)  0(4)  Sm(2)  0(10)  114.14(13)  0(4)  Sm(2)  0(12)  92.54(13)  0(6)  Sm(2)  0(10)  140.64(14)  0(6)  Sm(2)  0(12)  67.14(13)  0(10)  Sm(2)  0(12)  76.77(13)  0(3)  Sm(3)  0(4)  69.38(11)  0(3)  Sm(3)  O(ll)  70.86(12)  0(3)  Sm(3)  0(13)  146.48(12)  0(3)  Sm'3;  0(14)  126.60(12)  0(3)  Sm(3)  N(5)  74.03(13)  0(3)  Sm(3)  N(6)  119.08(13)  0(3)  Sm(3)  N(7)  78.73(13)  0(31  Sm(3)  N(8)  139.96(14)  0(4)  Sm(3)  O(ll)  72.96(13)  :  - 148-  Appendices  Table A12. Continued. atom  atom  angle  atom  atom  atom  angle  Sm(3)  0(13)  141.32(11)  0(4)  Sm(3)  0(14)  130.99(12)  Sn-.'3i  N(5)  105.29(13)  0(4)  • Sm(3)  N(6)  76.57(14)  Sm(3)  N(7)  148.10(13)  0(4)  Sm(3)  N(8)  74.24(13)  O(ll)  Sm'3.  0(13)  122.89(13)  0(11)  Sm(3)  0(14)  71.95(14)  0(11)  Sm(3)  N(5)  142.95(13)  O(ll)  Sm(3)  N(6)  141.36(14)  O(ll)  Sm(3)  N(7)  96.78(14)  O(ll)  Sm(3)  N(8)  83.13(14)  Sm[3)  0(14)  51.12(12)  0(13)  Sm(3)  N(5)  82.31(13)  0(13)  Sm(3)  N<6)  71.25(13)  0(13)  Sm(3)  N(7)  69.73(13)  0(13)  Sm(3)  N(8) .  73.42(14)  0(14)  Sm(3)  N(5)  123.31(13)  0(14)  Sm(3)  N(6)  113.81(14)  0(14)  Sm(3)  N(7)  69.39(13)  0(14)  Sm(3)  N(8)  68.58(13)  N(5)  Sm(3)  N(6)  68.30(13)  N(5)  Sm(3)  N(7)  64.66(13)  N(5)  Sm(3)  N(8)  132.98(14)  N(6)  Sm(3)  N(7)  121.40(14)  N(6)  Sm(3)  N(8)  65.98(14)  K(7)  Sm(3)  N(6)  135.69(14)  Sm(l)  0(1)  Sm(2)  110.79(15)  Sm(l)  O(l)  COD  119.0(3)  Sm(2)  O(l)  C(ll)  126.9(3)  Sm;j;  0(2)  Sm(2)  109.64(14)  Sm(l)  0(2)  C(24)  127.6(3)  Sm(2)  0(2j  C(24)  122.8(3)  Sm(2)  0(3)  Sm(3)  104.06(12)  0(3)  C(39)  128.4(3)  Sm(3)  0(3)  C(39)  125.8(3)  Sm(2)  0(4)  Sm(3)  101.55(11)  Sm(2)  0(4)  C(52)  131.5(3)  Sro(3)  0(4)  C(52)  125.1(3)  Sm(l)  0(5)  C(57)  136.9(4)  Sm(2)  0(6)  C(57)  139.2(4)  Sm(l)  0(7)  N(9)  96.2(3)  Smpfll  0(6)  N(9)  96.2(3)  Sm(2)  0(10)  C(59)  104.1(3)  Sm(3)  0(11>  C(59)  137,6(4)  Sm(2)  0(12)  C(61)  137.7(4)  Sm(3:  0(13)  N(10)  95.9(3)  Sm(3)  0(14)  N(10)  95.2(3)  Sm(l)  N(l)  C(l)  111.9(3)  Sm(l)  K(I):  C(3)  106.2(3)  Sm(l)  N(l)  C(9)  114.3(3)  C(l)  N(D  C(3)  108.3(4)  C(l)  NO)  C(9)  106.0(4)  C(3)  N(D  C(9)  110.0(4)  Sm(l)  N.'2,  C(2;  108.3(3)  Sm(l)  N(2)  C(16)  112.0(3)  Sm:(i^ii  N(2)  C(22)  109.3(3)  C(2)  N(2)  C(16)  108.7(5)  C(2,  M2)  C(22)  109:9(4)  C(16)  N(2)  C(22)  108.7(4)  Sm(l)  N(3)  C(4)  119.1(4)  Sm(l)  N(3)  C(8)  122 6(4)  C(4)  N(3)  C(8)  118.3(5)  Sm(l)  N(4)  C(17)  121.4(4)  Sm(l)  N(4)  C(21)  119.1(4)  C(17)  N(4)  C(21)  117:5(5)  atom  - 149-  Appendices  Table A12.  Continued.  atom  atom  atom  angle  atom  atom  atom  angle  Sin (3)  K(5)  C(29)  111.4(3)  Sm(3)  N(5)  C(31)  107.4(3)  Sm(3)  N(5)  C(37)  112.9(3)  C(29)  N(5)  C(31)  108.1(4)  C{29)  N(5)  C(37)  106.9(4)  C(31)  N(5)  C(37)  110.1(4)  Sm(3)  K(6J  C(30)  106 9(3)  Sm(3)  N(6)  C(44)  112.3(3)  Sm(3)  N(6)  C(50)  110.0(3)  C(30)  - N(6)  C(44)  106.7(5)  N(6)  C(50)  108.5(4)  C(44)  N(6).  C(50)  112.1(4)  Sm(3)  N(7)  C(32)  120.5(3)  Sm(3)  N(7)  C(36)  122.1(4)  C{32)  N(7)  C(36)  117.5(5)  Sm(3)  N(8)  C(45)  119.4(4)  Sm(3)  N(8)  C(49)  121.2(4)  C(4.5)  N(8)  C(49)  118.9(5)  N(9)  0(8)  117.0(5)  0(7)  N(9)  0(9)  122.2(6)  0(8)  N(9)  0(9)  120.7(6)  0(13)  N(10)  0(14)  117.5(5)  0(13)  N(10)  0(15)  120.9(6)  0(14)  N(10)  0(15)  121.5(5)  0(16)  N{H)  0(17)  120.7(11)  0(16)  N(ll)  0(16)  116.4(11)  0(17)  N(ll)  0(16)  120.7(10)  N(D  C(l)  C(2)  111.5(5)  N(2)  C(2>  C(l)  112.6(5)  K(D  C(3)  C(4) .  114.1(5)  N(3)  C(4)  C(3)  117.2(5)  K(3)  C(4)  C(5)  123.0(5)  C(3)  C(4)  C(5)  119.7(5)  C(4)  C(5)  C(6)  118.9(6)  C(5;  C(6)  C(7)  120-0(6)  C(6)  C(7)  C(8)  118.7(6)  N(3/  C(6)  C(7)  121.1(6)  K(D  C{9)  C(10)  114.9(4)  C(9,  CJ10)  C(ll)  118.4(5)  C(9)  C(10)  C(15)  121.8(5)  C(ll)  C(10)  C(15j  119:6(5)  0(1)  C(li)  C(10)  119.3(5)  0(1)  C(ll)  C(12)  121.2(5)  C(10)  C(U)  C(12)  119.5(5)  C(12)  C(13)  120.5(5)  C(12)  C(13)  C(14)  1194(6)  C(13)  C(14)  C(15)  120.2(6)  C{10)  C(15)  C(14)  120.7(5)  N(2)  C(16)  C(17)  113.2(5)  N(4)  C(17)  C(16)  115.9(5)  N<4)  C(17)  C(18)  1233(5)  C(16)  C(17)  C(18)  120.8(5)  C(17)  C(18)  C(19)  119.0(5)  C(18)  C(19)  C(20)  119.0(6)  C(19)  C(20)  C(21)  118.2(6)  N(4)  C(21)  C(20)  123.0(5)  N(2)  C(22)  C(23)  113.9(5)  C(22)  C(23)  C(24)  119.0(5)  C(22)  C(23)  C(28)  121.0(5)  C(24)  C(23)  C(28)  120.0(5)  0(7)  •  - 150-  Appendices  Table A12. Continued. atom  atom  atom:,  angle  atom  atom  atom  angle  0(2)  C(24)  C(23)  118.4(5)  0(2)  C(24)  C(25)  123.3(5)  C(23)  C(24)  C(25)  118.2(5)  C(24)  C(25)  C(26)  121.2(6)  C(25) .  C(26)  C(27)  120.4(6)  C(26)  C(27)  C(28)  119.7(5)  C(23)  C(28)  C(27)  120.2(5)  N(5)  C(29)  C(30)  111.0(5)  N(6)  C(30)  C(29)  111.9(5)  N(5)  C(31)  C(32)  115.9(5)  N("i  C(32)  C(31)  116.1(5)  N(7)  C(32)  C(33)  122.6(5)  coiy  C(32)  C(33)  121.0(5)  C(32)  C(33)  C(34)  118.9(5)  C(33)  C(34)  C(35)  120.2(5)  C(34)  C(35)  C(36)  117.1(5)  C(36)  C(35)  123.8(5)  N(5)  C(37)  C(38)  114.8(4)  C(36)  C(39)  119.5(5)  C(37)  C(38)  C(43)  121.6(5)  C(39)  C(3S)  C(43)  118.9(5)  0(3)  C(39)  C(38)  119.1(5)  0(3)  C(39)  C(40)  121.5(5)  C(38)  C(39)  C(40)  119.4(5)  C(39)  C(40)  C(41)  120.2(5)  C(40)  C(41)  C(42)  121.9(6)  C(41) .  C(42)  C(43)  118 8(5)  C(38)  C(43)  C(42)  120.9(5)  N(6) ,  C<44)  C.(45)  112,2(5)  N(8)  C(45)  C(44)  117.5(5)  N(6)  C(451  C(46)  120.1(6)  C(44)  C(45)  C(=J6)  122.3(6)  C(45)  C(40)  C(47)  119.4(6)  C(46)  C(47)  C(48)  119.6(6)  C<47)  C(48)  C(49)  119.1(6)  N(8)  C(49)  C(48)  122.9(6)  N(6)  C(50)  C(51)  112.3(5)  C(50)  C(51)  C(52)  119.0(5)  C(50)  C(51)  C(56)  121.2(6)  C(52)  C(51)  C(56)  119.7(6)  0(4)  C(52)  C(51)  120.6(5)  0(4)  C(52)  C(53)  120.6(5)  C(51)  C(52)  C(S3)  118:7(5)  C(52)  C(53)  C(54)  118.5(6)  C(53)  C(54)  C(S5)  121.4(7)  C(S4)  C(55)  C(56)  121.4(6)  C(51)  C(56)  C(55)  120.3(6)  0(5)  C(57)  0(6)  124.5(5)  0(5)  C(57)  C(58)  1187(5)  0(6)  C(57)  C(58)  116.8(5)  0(10)  C(59)  O(ll)  121.5(5)  0(10)  C(59)  C(60)  117.3(6)  O(ll)  C(59)  C(60)  121.2(6)  '  -151 -  Appendices  Table A13. Selected Crystallographic Data for [Fe(Ll)]N0 'CH OH. 3  [Fe(Ll)]N0 »CH OH  Complex  3  formula  C 9H 2FeN 06  fw  602.45  crystal system  monoclinic  space group  P2i/c  2  A  a,  3  5  10.2640(13) 14.7526(10)  b,A  A  18.3172(5)  A deg v, A z  97.9037(6)  c,  3  pcaic,  2747.3(3) 4  g/cm  3  1.456  T°C  -93  radiation  MoKa  A  X,  0.71069  cm"  1  p,  3  6.02  transm factor  0.8581-1.0000  /T  0.039  R  0.033  a w  R = T, \Fo\ - \Fc\l l\Fo\. R = (Ew(|F | - |Fc|) / 2  w  0  -  152-  YM\FO  3  Appendices  Table A14. Bond Lengths (A) and Bond Angles (deg) for [Fe(Ll)]N0 *CH OH. 3  3  atom  atom  distance  atom  , atom  distance  Fe(l)  od)  1.8610(14)  Fe(l)  0(2)  1.8855(15)  Fed)  Nd)  2.234(2)  Fe(l)  N(2)  2.228(2)  Fed)  N(3)  2.135(2)  Fe(l)  N(4)  2.135(2)  O(l)  C(ll)  1.336(3)  0(2)  C(24)  1.338(3)  0(3)  N(5)  1.215(3)  0(4)  N(5)  1.247(3)  O(S)  N(5)  1.237(3)  0(6)  C(29)  1.360(4)  0(6a)  C(29)  1.315(5)  N(l)  C(l)  1.490(3)  Nd)  C(3)  1.484(3)  N(l)  C(9)  1.496(3)  N(2)  C<2)  1.495(3)  N(2)  C(16)  1.485(3)  N(2)  C(22)  1.487(3)  N(3)  C(4)  1.339(3)  1.356(3)  N(4)  C(17)  1.352(3)  N(4)  C(21)  1.348(3)  C(l)  C(2)  1.511(3)  C(3.i  C(4)  1.500(3)  C(4)  C(5)  1.392(3)  C(5)  C(6)  1.366(4)  C(6)  C(7)  1.398(3)  C(7)  G(6)  1.368(3)  C(9)  C(10)  1.505(3)  C(10)  C(ll)  1.415(3)  C(10)  C(15)  1.380(3)  C(ll)  Cd2)  1.405(3)  C(12)  ,C(13)  1.393(4)  C(13)  Cd4)  1.375(4)  C(14)  C(15)  1.381(3)  Cd6)  C(17)  1.493(3)  C(17)  C(18)  1378(3)  C(18)  C(19)  1.399(3)  C(19)  C(20)  1.380(3)  C(20)  C(21)  1.383(3)  C(22)  C(23)  1.512(3)  C(23)  C{24)  1.422(3)  C(23)  C(28)  1.379(3)  C(24)  C(25)  1.400(3)  C(25)  C(26)  1.390(3)  C(26)  C(27)  1.383(3)  C(27)  C(28)  1.380(3)  atom  atom  atom  angle  atom  atom  atom  angle  O(l)  Fe(l)  0(2)  103.64(6)  O(l)  Fe(l)  N(l)  88.91(6)  O(l)  Fe(l)  N(2)  165.52(7)  O(l)  Fe(l)  N(3)  93.80(7)  0(1)  Fe(l)  N(4)  9321(7)  0(2)  Fe(l)  N(l)  164.93(7)  0(2)  Fe(l)  N(2)  88.77(7)  0(2)  Fe(l)  N(3)  93.37(7)  0(2)  Fe(l)  N(4)  96.88(7)  N(l)  Fe(l)  N(2)  80.04(7)  N(D  Fe(l)  N(3)  7728(7)  N(l)  Fe(l)  N(4)  90.59(7)  N(21  Fe(l)  N(3)  92.85(7)  N(2)  Fe(l)  N(4)  77.71(7)  -153 -  Appendices  Table A14. Continued. atom  atom  atom  angle  atom  atom  atom  Fe(l)  0(1)  C(ll)  angle 134.70(14)  N<3)  Fed)  N(4)  165.86(7)  Fe(l)  0(2)  C(24)  133.48(14)  Fe(l)  N(l)  C(l)  107.04(13)  Fed)  Nd)  C(3)  111.51(14)  Fe(l)  N(l)  C(9)  109.33(12)  Cd)  Nd)  C(3)  110.2(2)  Cd)  N(l)  C(9)  108.7(2)  C(3)  Nd)'  C(9)  110.0(2).  Fe(l)  N(2)  C(2)  106.65(13)  Fed)  N(2)  C(16)  110.50(13)  Fe(l)  N(2)  C(22)  108 94(13)  C(2)  N(2)  C(16)  110.7(2)  C(2)  N(2)  C(22)  109.2(2)  Cd6)  N(2)  C(22)  110.7(2)  Fe(l)  N(3)  C(4)  118.2(2)  Fed)'  N(3)  C(8)  122.6(2)  C(4)  N(3)  C(8)  118.7(2)  Fed)  N(4)  C(17)  118.07(15)  Fed)  N(4)  C(21)  123.4(2)  Cd7)  N(4)  C(21)  118.5(2)  0(3)  N(5)  0(4)  120.2(3)  0(3)  N(5)  0(5)  121.9(3)  0(4)  N(5)  0(5)  117.9(3)  N(D  C(l)  C(2)  109.1(2)  N(2)  C(2)  C(l)  109.4(2)  Nd)  C(3)  C(4)  113.7(2)  N(3)  C{4)  C(3)  117.9(2)  N(3)  C(4)  C(5)  121.4(2)  C(3)  C(4)  C(5)  120.7(2)  C(4)  C(5)  C(6)  119.4(2)  C(5)  C(6)  C(7)  119.6(3)  C(6)  C(7)  C(8)  118.1(2)  N(3)  C(8)  C(7)  122.7(2)  Nd)  C(9)  C(10)  114.4(2)  C(9)  C(10)  C(ll)  121.8(2)  C{9)  C(10)  C(15)  118.8(2)  C(U)  C(10)  P(15)  1193(2)  Od)  C(ll)  C(10)  122.5(2)  0(1)  C(ll)  C(12)  118.5(2)  COO)  C(ll)  C(12)  1190(2)  C(ll)  C(12)  C(13)  119.4(2)  C(12)  C(13)  C(14)  121.5(3)  C(13)  C(14)  C(15)  119.0(3)  COO)  C(15)  C(14)  121.8(3)  N(2)  C(16)  C(17)  114.2(2)  N(4)  C(17)  C(16)  116.7(2)  N(4)  C(17)  C(18)  122.3(2)  Cd6)  C(17)  C(18)  121.0(2)  C(17)  C(18)  C(19)  118.9(2)  C(18)  C(19)  C(20)  118.8(2)  C(19)  C(20)  C(21)  119.3(2)  N(4)  C(21)  C(20)  122.1(2)  N(2)  C(22)  C(23)  113.5(2)  C(22)  C(23)  C(24)  120.2(2)  C(22)  C(23)  C(2B)  120.7(2)  C(24)  C(23)  C(28)  119.2(2)  0(2)  C(24)  C(23)  122.1(2)  0(2)  C(24)  C(25)  119.2(2)  C(23)  C(24)  C(25)  118.6(2)  C(24)  C(25)  C(26)  120.4(2)  C(25)  C(26)  C(27)  120 7(2)  C(26)  C(27)  C(28)  119.1(2)  C(23)  C(28)  C(27)  122.0(2)  -154-  Appendices  Table A15. Selected Crystallographic Data for [ReO(Ll)]PF . 6  Complex  [ReO(Ll)]PF  formula  C 8H F N40 PRe  fw  799.71  crystal system  monoclinic  space group  P2/c  a, A  11.9219(4)  b,k  10.1817(4)  c, a,  6  2  28  6  3  A  12.7269(4)  deg  90.000(1)  A deg  111.001(1)  7, deg  90.000(1)  V, A  1442.24(9)  3  2  Z p , g/cm  1.842  r,°c  -100  /LA  0.71073  transm factor  0.632904-1.0000  3  ca/c  0.0186 wR  a 2  /? = I | | F O | - | F C | / E | F O | .  0.0505 WRI = (z[w(Fo  2  -Fc ) ]/2Z[w(Fo ) ]y 2  -155 -  2  2  2  Appendices  Table A16. Bond Lengths (A) and Bond Angles (deg) for [ReO(Ll)]PF . 6  Re(1)-0(2) Red)-O(l) Red) -N(2)#l Red) -N(l) N(2)'-"C(5) N ( l ) -C(6) N ( l ) -C(7) P(l) -F(2)#2 P(l) -F(3) P(l)-F(l)#2 P(1D)-F(4D) P (ID) -F(5D) P(1D)-F(1D)#2 C(l) -C(6) C(2)-H(2) C(3) -H(3) C(4)-H(4) C(6)-H(6B) C(7)-C(8) C(7) H(7B) C(8)-C(9) C(10)-C(ll) C(ll)-C(12) C(12)-C(13) C(13)-H(13) C ( 1 4 ) -HC14B) 7  0(2)-Re(l)-0(1)#1 0(1)#1-Re(1)-0(1) 0(1)#1-Re(1)-N(2) 0(2.)-Re(l)-N(2)#l O(l)-Re(1)-N(2>#1 0(2)-Re(l)-N(l)#l 0(1)-Re(l)-N(l)#l N(2) # 1 - R e ( l ) - N ( l ) # l 0(1)#1-Re(l)-N(l) N{2)-Re(1)-N(l) N(l)#l-Re(l)-N(l) C(5) -N(2) - C ( l ) C ( l ) -N(2) - R e ( l ) C(6) - N ( l ) -C(7) C(6)-N(l)-Re(l) C(7)-N(l)-Re(1) F(2)-P(l)-F(3)#2 F(2)-P(l)-F(3) F(3)#2-P(l)-F<3) F(2)#2-P(1)-F<1) F(3)-P(l)-F(l) F(2)#2-P(l)-F(l)#2 F(3)-P(l)-F(l)#2  1 .689(3) 2 .002(2) 2 .257(2) 2 .363 (2) 1 .345 (4) 1 .494 (4) 1 .521(4) 1 .574 (4) 1 .575(4) 1 .588 (4) 1 .569(6) 1 .573(5) 1 .576(5) 1 .484 (4) 0 .90(4) 0 .95 0 .95 0 .99 Al .505(4) 0 99 1 .397(4) 1 388 (5) 1 380(5) 1 396(5) 0 95 0 99 1  Re(l)-0(1)#1 Re(l)-N(2) Re(l)-N(l)#l 0(1)-C(9) N(2)-C(l) N(l)-C(14) P(l)-F(2) P(l)-F(3)#2 P(l)-F(l) P(1D) - F ( 6 D ) P(1D)-F(5D>#2 P(1D)-F(1D) C(l)-C(2) C(2)-C(3) C(3)-C(4) C(4)-C(5) C(5)-H(5) C(6) -H(6A) C(7)-H(7A) C(8)-C(13) C(9) -C(10) C(10) -H(10) C(ll)-H(ll) C{12)-H(12) C(14)-C(14)#l C(14)-H(14A)  101 .73(6) 0 ( 2 ) - R e ( l ) - 0 ( 1 ) 156 . 5 4 ( 1 2 ) 0 ( 2 ) - R e ( l ) - N ( 2 ) B7 . 0 4 ( 8 ) 0 ( 1 ) - R e ( l ) - N ( 2 ) 76 . 4 0 ( 6 ) 0 ( 1 ) # 1 - R e ( l ) - N ( 2 ) # l 87 . 0 4 ( 8 ) N ( 2 ) - R e ( l ) - N ( 2 ) # l 143 . 5 9 ( 6 ) 0 ( 1 ) # 1 - R e ( l ) - N ( l ) # l 80 . 6 0 ( 8 ) N ( 2 ) - R e ( l ) - N ( l ) # l 67 . 3 8 ( 8 ) 0 ( 2 ) - R e ( l ) - N ( l ) 80 . 6 0 ( 8 ) 0 ( 1 ) - R e d ) - N ( l ) 67 . 3 8 ( 8 ) N ( 2 ) # l - R e ( l ) - N ( l ) 72 . 8 3 ( 1 1 ) C ( 9 ) - 0 ( 1 ) - R e ( l ) 118 . 2 ( 3 ) C(5)-N(2)-Re(l) 120 .7 (2) C(6)-N(l)-C(14) C(14)-N(l)-C(7) 109 .4 (2) 106 . 9 ( 2 ) C(14)-N(l)-Re(l) 113 . 7 ( 2 ) F(2)-P(l)-F(2)#2 177 . 1 ( 4 ) F(2)#2-P(l)-F(3)#2 91 .5(3) F(2)#2-P(l)-F(3) 90 . 7 ( 5 ) F(2)-P(l)-F(l) 93 . 6 ( 5 ) F(3)#2-P(l)-F(l) 68 . 4 ( 4 ) F(2)-P(l)-F(l)#2 88 . 0 ( 4 ) F(3)#2-P(l)-F(l)#2 90 . 1 ( 4 ) F(l)-P(l)-F(l)#2  -156-  2 .002(2) 2 .257(2) 2 .363 (2) 1 .361(4) 1 .350(4) 1 -494 (3) 1 .574 (4) 1 .575(4) 1 .588 (4) 1 .558(6) 1 •573(5) 1 .576(5) 1 .384(5) 1 .383(5) 1 .374(5) 1 .379(4) 0 . 95 0 .99 0 .99 1 .387(4) 1 .399(4) 0 .95 0 .95 0 .95 1 .500(6) 0 .99 1 0 1 73 ( 6 ) 76 4 0 (6) 98 4 7 ( B ) 98 4 7 ( 8 ) 152 80 (12) 8 0 57 ( 8 ) 1 3 9 . 73 ( 9 ) 1 4 3 58 ( 6 ) 8 0 . 57 ( 8 ) 1 3 9 . 73 ( 9 ) 112 8 ( 2 ) 121 1(2) 107 7 ( 2 ) 107. 2(2) 111. 7(2) 86. 5(4) 91. 5(3) 1 7 7 . 1 (3) 88 . 0 ( 4 ) 90. 1(4) 93. 6(5) 88. 4 (4) 177 8 ( 8 )  Appendices  Table A16. Continued. 91. 1(4)  180. 000(2)F(6D) - P U D ) -F(5D)#2  F(6D) - P U D ) -F(4D) F(4D)-P(1D)-F(5D)#2  88. 9(4)  F(6D) - P U D ) -F(5D)  F(4D)-P(1D)-F(5D)  88. 9(4)  F(5D)#2-P(1D)  F(6D) -P(1D)  92  91. 1(4) 177. 7(9)  -F(5D)  8(9)  F(4D) - P U D ) - F U D )  B7. 2(9)  F(5D)#2-P(1D)-F(1D)  89. 5(9)  F(5D) - P U D ) - F U D )  90. 4(9)  F(,6D)-P(1D)  92. 8(9)  F(4D) - P U D )  90. 4(9)  F(5D)-PUD)-F(1D)#2  -F(1D) -F(1D)#2  F(5D)#2-P(1D)-F(1D)#2 F U D ) - P ( 1 D ) - F U D )  #2  174  (2)  87. 2(9)  - F U D ) # 2 .  89. 5(9)  N ( 2 ) - C U ) - C ( 2 )  122. 0(3)  N ( 2 ) - C ( l ) - C ( 6 )  113. 0(3)  C ( 2 ) - C U ) - C ( 6 )  125. 0(3)  C ( 3 ) - C ( 2 ) - C ( l )  118. 9(3)  C(3) -C(2)  -H(2)  121  C ( l ) - C ( 2 ) - H ( 2 )  120  C(4) -C(3)  -C(2)  119. 4  (3)  C(4)-C(3)-H<3)  120. 3  C(2) -C(3)  -H(3)  120. 3  (2)  C(3) -C(4)  1 1 8 . 9.(3)  C(3)-C(4)-H(4)  120. 6  (2)  120. 6(2)  N(2)-C(5)-C(4)  122  6  (3)  N(2)-C(5)-H(5)  118. 7(2)  C(4)-C(5)-H(5)  118  7(2)  C(l)-C(6)-N(l)  107  C U )  110  3  (2)  N U ) - C ( 6 ) - H O B )  110.3(2)  i i o  3  (2)  108  5  -C(5)  C(S) -C(4) -H(4)  ;;:  (3) (2)  2(2)  -C(6)  -H(6B)  C U ) - C ( 6 ) - H ( 6 A )  (3)  N U ) - C O ) - H ( 6 A )  110  27(14)H(6B)-C(6)-H(6A)  C(8)-C{7)-N(l)  116  108  3  (2)  108  C(8)-C(7)-H(7A) 1(2) 26U4)C(8)-C(7)-H(7B)  108  3  (2)  108  26(14)H(7A)-C(7)-H(7B)  107  4  N(l)  -C(7) -H(7A)  N U ) - C ( 7 ) - H ( 7 B )  119  7(3)  C(13)-C(8)-C(7)  122  C ( 9 ) - C ( 8 ) - C ( 7 )  117  8  0(1)  120  0(1)-C(9)-C(10)  119  8(3)  C(B) - C O ) - C U 0 )  120 .0(3)  C ( l l )  -C(10) - C O )  119 .3(3)  C ( l l ) - C U O ) - H U O )  120 .4(2)  - C ( 1 0 ) - H (10)  120 .4(2)  C(12) - C U D  C ( 1 2 ) - C ( l l ) - H ( l l )  119 .5(2)  C110) - C U D - H U D  119  5  (2)  C ( l l )  119 .5(3)  C U D  120 .2  (2)  120 .2  C(8) - C U 3 ) - C U 2 )  120  4  (3>  C (12)  119 .8  (2) (2)  C(13) -C{8)  C O )  - C O )  - C U 2 ) - C U 3 )  C U 3 0 -C(12) C ( 8 ) - C U 3 )  -H(12) - H U 3 )  119  (3)  (2)  8(2)  - C O ) -C(B)  -C(10)  - C U 2 ) - H U 2 ) - C U 3 ) - H U 3 )  4  121 .1(3)  108 ..4(2)  N U )  - C U 4 )  - H U 4 B )  110 .0  C(14)#1-C(14)-H(14B)  110,0  N U )  - C U 4 )  - H U 4 A )  110 .00  C(14)#l-C(14)  110 . 0 0 ( 1 2 ) H ( 1 4 B ) - C U 4 )  N ( l ) - C ( 1 4 )  - C U 4 ) # 1 - H U 4 A )  (2)  - H U 4 A )  Symmetry transformations used to generate equivalent atoms #1 -x+l,y«-z+l/2  #2 -x,y,-z+1/2  - 157-  (3)  .1(3)  108 .4  (14)  

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