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Magnetic and spectral studies of some polynuclear carboxylates of copper (11) Lin, Yun-Chi 1965

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MAGNETIC AND SPECTRAL STUDIES OF SOME POLYNUCLEAR CARBOXYLATES OF COPPER (11) by YUN - CHI LIN M.Sc, National Taiwan University, i 9 6 0 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF • MASTER OF SCIENCE i n the Department of Chemistry We accept t h i s thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA November, 1965 In p r e s e n t i n g t h i s t h e s i s i n p a r t i a l f u l f i l m e n t o f the r e q u i r e m e n t s f o r an advanced degree a t t h e U n i v e r s i t y o f B r i t i s h C o lumbia, I a g r e e t h a t t h e L i b r a r y s h a l l make i t f r e e l y a v a i l a b l e f o r r e f e r e n c e and s t u d y . I f u r t h e r a g r e e t h a t p e r -m i s s i o n f o r e x t e n s i v e c o p y i n g o f t h i s t h e s i s f o r s c h o l a r l y p u r p o s e s may be g r a n t e d by the Head o f my Department o r by h i s r e p r e s e n t a t i v e s . I t i s u n d e r s t o o d t h a t c o p y i n g o r p u b l i -c a t i o n o f t h i s t h e s i s f o r f i n a n c i a l g a i n s h a l l not be a l l o w e d w i t h o u t my w r i t t e n p e r m i s s i o n . Department o f l . ' S h y j ) y^U % Vw\ The U n i v e r s i t y o f B r i t i s h Columbia Vancouver 8, Canada i ABSTRACT Magnetic s u s c e p t i b i l i t y studies over the temperature range 8?-330°K, on sixteen complexes of copper (11) are reported. The compounds are conveniently divided i n t o two groups. Group I compounds ( copper (11) benzoate and i t s monopyridine adduct, copper (11) meta-chlorobenzoate and i t s monopyridine and mono-p-dioxane adducts and the monopyridine and hemipyridine adducts of copper (11) para-chlorobenzoate ) possess magnetic properties expected f o r a binuclear system and values of the exchange i n t e g r a l s have been calculated, f o r these compounds. The group 11 compounds ( the di p y r l d l n e adducts and the basic s a l t s of copper ( l l ) benzoate, copper (11) ortho-, meta- and para-chlorobenzoate ) exhibit only weak magnetic i n t e r a c t i o n t h e i r magnetic s u s c e p t i b i l i t i e s obeying the Curie-Weiss law with small Weiss constants — • and they are considered to have polymeric structures. Copper (11) para-chlorobenzoate exhibits properties i n t e r -mediate between the group I and 11 compounds. Confirmatory evidence f o r assigning binuclear structures to the group I compounds has been obtained from the presence, i n the spectra of the group I compounds, of a band at about 400 nni which i s absent from the spectra of the group 11 com-pounds. Infrared spectra are reported f o r a l l the compounds studied and a p a r t i a l assignment has been made. i i ACKNOWLEDGMENTS The author i s g r a t e f u l to Dr. Robert C. Thompson, his supervisor, f o r h i s generous encouragement and kind guidance. Thanks are also made to Dr. Murray of the B. C. Research Council f o r allowing use of the Cary 14 Spectrophotometer f o r the d i f f u s e - r e f l e c t a n c e measurements, and to Miss Caroline Jenkins i n the microanalytical laboratory of thi s Department f o r the carbon, hydrogen and nitrogen microanalyses. i i i TABLE OP CONTENTS Page Abstract i Acknowledgments i i L i s t of Tables V L i s t of Figures V i i Chapter!. Introduction. I Chapter I I . Experimental. 13 2-1. Preparation of Copper (11) Complexes. 13 2-1-1. Aryl-Carboxylates. 15 2-1-2. Basic Salts of Aryl-Carboxylates. 16 2- 1-3. Dioxane and Pyridine Adducts of A r y l -Carboxylates. 16 2-2. Preparation of Sodium Aryl-Carboxylates. 19 2-3. P u r i f i c a t i o n of Solvents. 19 2-4. Analyses. 19 2-5. Magnetic S u s c e p t i b i l i t y Measurements. 19 2-6. Diffuse-Reflectance Spectra. 21 2- 7. Infra-red Absorption Spectra. 21 Chapter I I I . Results and Discussion. 22 3- 1. Magnetic S u s c e p t i b i l i t y Studies. 22 3- 1-1. Copper (11) Aryl-Carboxylates and t h e i r Monopyridine and Monodioxane Adducts. 22 3-1-2. Dipyridine Adducts of Copper (11) Aryl-Carboxylates. 41 IV Page 3 - 1 - 3 / Basic Salts of Copper (11) A r y l -Carboxylates. 48 3-2. Diffuse-Reflectance Spectra of Anhydrous Copper (11) Aryl-Carboxylates and Related Compounds. 54 3-3» Infrared Spectra of Anhydrous Copper (11) Aryl-Carboxylates and Related Compounds. 65 -1 3-3-1. 4000 - 1800 cm. region. 65 3-3-2. 1800 - 1300 cmT1 region. 66 3-3-3. 1300 — 800 cmT1 region. 69 3-3-4. 800 — 400 cmi 1 region. 69 Bibliography. 83 V LIST OP TABLES Page A n a l y t i c a l data. 13 Room-temperature magnetic data f o r copper (11) aryl-carboxylates and re l a t e d com-pounds. ' 27 Calculated values of g, Tc, J , ^ H°and ^ S* f o r [CU(X-C DH2J,C0 2)2 ,L] 2 • 28 Experimental gram and molar s u s c e p t i b i l i t i e s , magnetic moments and equilibrium constants f o r the s i n g l e t - t r i p l e t interconversion f o r anhydrous copper (11) aryl-carboxylates and r e l a t e d compounds. 29 Room-temperature magnetic data f o r d i p y r i -dine adducts of copper (11) aryl-carboxylates. Experimental gram and molar s u s c e p t i b i l i t i e s and magnetic moments f o r dipyridine adducts of copper (11) aryl-carboxylates. 45 Room-temperature magnetic data f o r basic s a l t s of copper (11) aryl-carboxylates. 50 Experimental gram and molar s u s c e p t i b i l i t i e s and magnetic moments f o r basic s a l t s of copper (11) aryl-carboxylates. 51 Diffuse-reflectance spectra. 60 Vi Tables Page X -I.E. absorption frequencies i n some sodium carboxylates. 71 XI I.E. absorption frequencies i n anhydrous copper (11) aryl-carboxylates. 73 XII I.E. absorption frequencies i n basic salts of copper (11) aryl-carboxylates. 75 XIII I.E. absorption frequencies i n monopyridine adducts of copper (11) aryl-carboxylates. 77 XIV I.E. absorption frequencies i n dipyridine adducts of copper (11) aryl-carboxylates. 79 XV Most important frequencies found i n infrared absorption spectra of copper (11) ary l -carboxylates and related compounds. 82 •J V i i LIST OP FIGURES Figures Page 1 Cryomagnetic data f o r copper (11) benzoate. 33 2 Cryomagnetic data f o r copper (11) meta-ohlorobenzoate. 34 3 Cryomagnetic data f o r copper (11) para-chlorobenzoate. 35 4 Cryomagnetic data f o r copper (11) benzoate monopyridine. 36 5 Cryomagnetic data f o r copper (11) meta-ohlorobenzoate monopyridine. 37 6 Cryomagnetic data f o r copper (11) para-chlorobenzoate monopyridine. 38 7 Cryomagnetic data f o r copper (11) para-chlorobenzoate hemipyridine. 39 8 Cryomagnetic data f o r copper (11) meta-chlorobenzoate mono-p-dioxane. 40 9 Proposed polynuclear structures f o r the dipy r i d i n e adducts of copper (11) a r y l -carboxylates. 42 10 Cryomagnetic data f o r the dipyridine adducts of copper (11) aryl-carboxylates. 47 V i i i Page Proposed structure f o r the basic s a l t s of copper (11) aryl-carboxylates. 49 Cryomagnetic data f o r the basic s a l t s of copper (11) aryl-carboxylates. 53 Diffuse-reflectance spectra f o r anhydrous copper (11) aryl-carboxylates. 61 Diffuse-reflectance spectra f o r monopyridine, hemipyridlne and p-dioxane adducts of copper (11) aryl-carboxylates. 62 Diffuse-reflectance spectra f o r dipyridlne adducts of copper (11) aryl-carboxylates. 63 Diffuse-reflectance spectra f o r basic s a l t s of copper (11) aryl-carboxylates. 64 I Magnetic and Spectral Studies of Some Polynuclear Carboxylates of Copper (11) Chapter I . Introduction The carboxylates of copper (11) have been the subject of extensive i n v e s t i g a t i o n over the past ten years. With the one known exception of copper (11) s a l i c y l a t e tetrahy-21 drate these compounds a l l appear to be polynuclear. Mar-45 46 t i n and Waterman pointed out three ways i n which the car-boxylate group can bridge copper ions to form polynuclear com-plexes. O — Cu Cu ^ „ C u ^ B-C R — C R-C \ O-Cu _ /0 O-Cu Cu syn-syn anti-syn a n t i - a n t i I II I I I Examples of a l l three configurations are known. Copper (11) acetate monohydrate i t s structure determined by van Niekerk and 6? Shoening J from X-ray c r y s t a l analysis, has configuration I . The structual feature of t h i s compound i s that the copper atoms are bridged In p a i r s by four acetate groups to form binuclear molecules, Cu 2( ; 9 H 3 C 0 2 ) 4 e 2 H 2 ° » with the two water molecules occupying terminal positions on the copper atoms. Copper (11) acetate monopyridine^ has an analogous structure i n which 2 pyridine molecules occupy the positions of the water molecules i n the monohydrate de r i v a t i v e . In copper (11) formate t e t r a -32 hydrate-' , X-ray studies have shown that each copper atom i s bridged to two d i f f e r e n t copper atoms by carboxylate groups i n the a n t i - a n t i configuration I I I . Antl-syn carboxylate bridging, I I s has been found i n the royal-blue form of anhydrous copper (11) 2 formate where, each copper atom i s joined to four d i f f e r e n t copper atoms by bridging formate groups. Copper (11) benzoate t r i h y d r a t e ^ also has a polymeric structure, i n which each copper atom i s bridged by one benzoate group and two water molecules to two d i f f e r e n t copper atoms, forming l i n e a r chains [cu(C5H5C02)• between them. These compounds exhibit i n t e r e s t i n g magnetic properties,*. Copper (11) acetate monohydrate ->s i s characterised by a sub-normal moment of 1.40 B.M. at room temperature ( magnetically 1 ? d i l u t e copper (11) compounds have moments l y i n g i n the range 1.8 - 2.0 B.M. ). The OCm - T curve f o r t h i s compound goes through a maximum at 255°K i above t h i s temperature the suscep-t i b i l i t y decreases gradually following the Curie-Weiss law ; below t h i s temperature the s u s c e p t i b i l i t y decreases with tem-perature and reaches a constant value 9 60 x 10"^ emu., near l i q u i d nitrogen temperature. This antiferromagnetism has been explained i n terms of the formation of a weak 8-bond by the overlap of 3 d z 2 _ y 2 o r b i t a l s on the two copper atoms i n the 3 binuclear u n i t . The p o s s i b i l i t y of bond formation by overlap of 3 d z2 o r b i t a l s was rejected on the grounds that the promo-tio n energy needed to a t t a i n t h i s i s 12,000 cm!1. A subnormal moment was also observed f o r copper (11) f o r -mate t e t r a h y d r a t e ^ s ^ j ^ f c ' . I t s OCm"1 - T curve obeys the Curie-Weiss law with a Weiss constant of -175°K which indicates considerable spin Interaction i n the molecule, but the i n t e r -action i s r e l a t i v e l y weak with respect to that which occurs i n copper (11) acetate monohydrate. Accordingly, a superexchange mechanism which occurs v i a the formate bridging groups i s suggested to give r i s e to the i n t e r a c t i o n between the copper Ions. On the other hand, the royal-blue form of the anhydrous copper (11) formate*^ shows a normal magnetic moment. I t s QCm-l - T curve obeys the Curie law i n the temperature range from 100 to 330°K. Copper (11) benzoate trihydrate 25»26,42 has also been shown to have a normal magnetic moment at room temperature. I t s magnetic s u s c e p t i b i l i t y obeys the Curie-Weiss law over the temperature range 100-300°K with a Weiss constant of -15°K, i n d i c a t i n g only weak int e r a c t i o n s occur i n the molecule. The r e l a t i v e l y large antiferromagnetlc Interaction obser-ved i n copper (11) acetate monohydrate Is i n good agreement 0 with the short copper - copper distance ( "^Cu-Cu = 2.64 A ) i n the molecule, but an explanation, i n terms of the shortest copper - copper distance, f o r the difference i n magnetic 4 properties of the royal-blue form of anhydrous copper (11) formate, the tetrahydrated copper (11) formate and the t r i -hydrated copper (11) benzoate does not appear possible ( The shortest copper - copper distances i n these complexes are o 3.44, 5.80 and 3.15 A, respectively. ). In the absence of d e t a i l e d X-ray crystallographlc re-s u l t s , the magnetic properties are often used as a guide i n the structual assignments of copper (11) carboxylates and rela t e d compounds. Thus, M a r t i n i ^5 et a l . concluded on the basis of s i m i l a r i t i e s i n magnetic properties with the dimeric copper (11) acetate monohydrate that copper (11) acetate and i t s higher homologs have binuclear structures. In l i n e with t h i s , Kubo 1 et a l . reported that the <^,uLdicarboxylates of copper (11) of the type, Cu(oCO(CH2 ) n OCo) 2 (n=2-10) which show subnormal moments at room temperature ( A I = 1 . 3 3 - 1*^5 B.M. ) also have dimeric structures i n the c r y s t a l l i n e state. Lewis and Thompson^ came to the same conclusion that copper (11) benzoate and the substituted benzoates with room-temperature moments of 1 . 4 + 0 . 0 5 B.M. are l i k e l y to have binuclear struc-tures. A l t e r n a t i v e l y , copper (11) formate^, copper (11) t r i h a l o -genoacetate3^y6l and copper (11) m a l o n a t e 1 * ^ show room-tempe-rature moments higher than the spin-only value, M = 1 . 7 3 B . M . , f o r one unpaired electron. Since t h i s magnetic behavior i s s i m i l a r to that of magnetically d i l u t e copper (11) s a l t s , i t 5 i s f e l t that these compounds do not have binuclear structures. There are instances, where more than one magnetically d i s t i n c t form of the same compound have been prepared. Thus, as many as f i v e magnetically d i f f e r e n t modifications of copper (11) benzoate 2 2,2 6 ,42 , 4 3 have been found. Their room-tempe-rature moments vary from 1.40 to 1.78 B.M.. The formation of these d i f f e r e n t modifications depends upon the method of pre-paration and the choice of s t a r t i n g materials. Recently considerable i n t e r e s t has centred on the adducts of copper (11) carboxylates with Lewis bases. I t has been found that where the anhydrous copper (11) carboxylate exhibits only weak magnetic i n t e r a c t i o n coordination with a strong Lewis base ( e.g. pyridine ) r e s u l t s i n an increase i n the magnetic i n t e r a c t i o n . Thus, the monopyridine adducts of copper (11) ortho-bromobenzoate^S and copper (11) ortho-chlorobenzoate?0 have room-temperature moments of 1.37 and 1.32 B.M., respect-i v e l y , considerably below the values observed f o r the corres-ponding anhydrous compounds. This behavior has been explained i n terms of a change from a polynuclear structure i n the anhy-drous compounds to a dimeric structure i n the adducts with an accompanying increase i n the magnetic i n t e r a c t i o n . The organic ligands, g-dloxane, p i c o l i n e and urea were found to exhibit the same property as pyridine i n " conditioning w polymeric carboxylates of copper (11) i n t o dimeric compounds. Thus, the monourea adduct33»34 and the three isomeric monopicollne 6 adducts^? of copper (11) formate were reported to show sub-normal room-temperature moments considerably smaller than that of the o r i g i n a l anhydrous copper (11) formate. Sim i l a r -l y 9 the hemidioxane adduct^7 of copper (11) formate has a room-temperature moment of O.96 B.M., On the other hand, i f the anhydrous copper (11) carboxy-l a t e has a binuclear structure i n most cases i t has "been found that the addition of one molecule of Lewis base per copper atom has very l i t t l e e f f e c t on the magnetic properties of the molecule. For example, the formation of adduct-complexes with benzoic acid, dioxane, ethanol, methanol, pyridine, p i c o l l n e and urea does not change the magnetic moment of binuclear anhy-drous carboxylates of copper (11) very much, as i s seen from the r e s u l t s of Gilmour 1?, Inoue24 ,25,26 f Kishi t a 3 3 , 3 ^ , Lewis^2 s M a r t i n ^ 2 * ? , Scott58 9 Wilkinson 6 5 and Yawney70. An exception to t h i s generalization appears i n the a n i l i n e and t o l u i d i n e a d d u c t s ^ with the binuclear copper (11) n-alkanoates. In these cases the magnetic i n t e r a c t i o n i s decreased considerably on coordination with base. Several Dipyridine adducts of copper (11) carboxylates have been reported. W i l k i n s o n ^ e t a l . found that the d i p y r i -dine adducts of copper (11) benzoate and copper ( l l ) formate show normal room-temperature moments, ;u = 1.88 - 1.91 B.M.. S i m i l a r l y , Satake56 e t a l . succeeded i n preparing the d i p y r i -dine adducts of copper (11) stearate ( /a = 1.80 B.M. ). 7 In 1957 Tsuchlda 0^ and coworkers reported the p o l a r i z e d absorption spectra of some dimeric and polymeric copper (11) n-alkanoates i n the c r y s t a l l i n e state. In the case of the dimeric compounds, the spectra were measured along two mutu-a l l y perpendicular di r e c t i o n s | one i n the Cu(0zj.) plane and the other along the copper to copper ax i s . The r e s u l t s i n d i -cate that copper (11) acetate monohydrate, copper (11) n-pro-pionate, and copper (11) n-propionate monohydrate, which have dimeric structures, show two intense absorption bands at ca. 700 and 375 mu, whereas polymeric copper (11) formate t e t r a -hydrate has only one maximum absorption at ca. 790 mu. The i n t e n s i t i e s of the two bands found f o r the dimeric compounds are much greater than the band i n t e n s i t i e s observed f o r nor-mal mononuclear copper (11) s a l t s . Moreover, the r a t i o of band i n t e n s i t y i n the Cu(O^) plane to that i n the d i r e c t i o n of Cu-Cu axis i s about ten f o r the band at ca. 700 vap. and about one tenth f o r the other band. Thus, they concluded that the appearance of the band at 375 mu, combined with i t s p o l a r i z a t i o n property, may be regard as evidence f o r the existence of a binuclear molecule. Graddon^-8,19 found that copper ,(11) n-alkanoates other than copper (11) formate and copper (11) /3-diketones have analogous e l e c t r o n i c absorption spectra In ethanol, and he t e n t a t i v e l y assigned the bands at 700 and 375 rap. f o r the copper (11) n-alkanoates to the d : x y —» d x 2 - y 2 a n d ( d x z , d y Z ) — » d x 2 - y 2 t r a n s i t i o n s , r e s p e c t i v e l y . 8 The assignment was given on the assumption that both bands are due to the d-d t r a n s i t i o n s of the cupric i o n . A d i f f e -rent assignment was given by Basu^, who considered that the band at 375 mu may be due to a ligand t r a n s i t i o n rather than a d-d t r a n s i t i o n on the basis of h i s work on copper (11) substituted /3-diketones. In 1964, Yamada31 et a l . reexa.m1.ned the spectrum of copper (11) acetate and assigned the bands at ca. 700 and 375 mu to the ( d X Z j d y z ) — ) • d2.2_.y2 and d z 2 — } d x 2 - y 2 t r a n s i t i o n s , res-p e c t i v e l y . Reimann55 et a l . , i n I 9 6 5 , found a new band at 999 p i n addition to the bands at 700 and 375 nyi f o r copper (11) acetate monohydrate. They assigned these three bands at 999* 700 and 375 mu to the d x y — » d x 2 _ y 2 , ( d X Z j d y z ) — » d x 2 - y 2 and d z 2 — > d x 2 _ y 2 t r a n s i t i o n s , r e s p e c t i v e l y . From a l l the r e s u l t s described above, the band at ca. 700 mu found f o r the dimeric copper (11) carboxylates Is unquest^iably a t t r i b u t a b l e to a d-d t r a n s i t i o n of the cupric i o n , whereas the o r i g i n of the band at ca. 375 W- remains questionable. A number of observations have been made which show that copper (11) n-alkanoates ( with the exception of copper (11) formate ) and t h e i r monoadducts with Lewis bases, show two absorption bands s i m i l a r to the ones observed f o r copper (11) acetate monohydrate i n the v i s i b l e region and the r e s u l t s i n d i c a t e that the band at longer wave lengths ( band I ) i s sens i t i v e to the v a r i a t i o n of the carboxylate group whereas 9 the other band at shorter wave lengths ( band 11 ) i s insen-s i t i v e . The sensitiveness of band I toward the v a r i a t i o n of the carboxylate group can be seen c l e a r l y from the following 66967 . band I at 770 mu f o r copper (11) acetate s h i f t s to 696 mu f o r copper (11) n-propionate and to 679 nyu f o r copper (11) stearate i n alcohol. The e f f e c t of solvent on the p o s i -t i o n of the absorption maximum of band I can be seen from the spectra of dimeric copper (11) n-alkanoates^S. These compounds i n ethanol show band I at 690 + 11 mu which s h i f t s to 675 mu i n benzene and to 665 + 10 mju i n dioxane. Dimeric copper (11) aryl-carboxylates^ 2958,69,70 i n the c r y s t a l l i n e state and i n non-donor and donor solvents such as benzene, chloroform, dioxane and ethanol also show i n the v i -s i b l e region two absorption bands which are i n close confor-mity with those observed f o r the dimeric copper (11) n-alka-noates. In dioxane, an intense band at 690 - 710 m;i and a weak band at 38O mu t»7ere found i n the v i s i b l e region by Yamada6? et a l , f o r copper (11) benzoate and copper (11) substituted benzoates which included the ortho, meta, and para losmers o f the chloro, hydroxyl, methyl, methoxyl and n i t r o d e r i v a t i v e s . The r e s u l t indicates that band I i s sensi t i v e to the strength of the liga n d f i e l d surrounding the cupric i on and band 11 i s i n s e n s i t i v e . In general, band I s h i f t s to shorter wave lengths with increasing donor strength of the ligand. In the crysta-l l i n e state, several anhydrous and hydrated copper (11) a r y l -c a r b o x y l a t e s ^ 2 * ^ a r e now known to show two absorption bands 10 at 658-682 and 370 - 417 mu0 These include the benzoate ( p . = l o 4 0 BoM<> ) , ortho-niethylbenzoate 9 ortho-chlorobenzoate dihydrate and meta-hydroxy1 benzoate monohydrate of copper ( 1 1 ) . Two absorption bands were also found i n several dimeric copper (11) aryl-carboxylates of the type (CU(0C0R)2°L] 2 where L represents benzoic a c i d s ethanol, pyridine and, | ( 4 , V - d l p y r l d y l ) ^ 2 , 5 8 , 7 0 . I t i s i n t e r e s t i n g to note that the i n t e n s i t y of band I of dimeric copper (11) carboxylates decreases and at the same time band 11 disappears, i f the spectra are measured i n strongly coordinating medium such as water or pyridine where the b i -nuclear structure i s destroyed. In resemblance to copper (11) formate tetrahydrate, other polymeric copper (11) carboxylates also show only one d-d . t r a n s i t i o n band i n the v i s i b l e region. Several compounds belonging to t h i s category are now known. They are the anhydrous formate^ 9 t r i c h l o r o a c e t a t e ^ benzoate t r i h y d r a t e ^ 2 9 ortho-bromobenzoate58 and ortho-chlorobenzoate70 of copper ( 1 1 ) . However, these polymeric copper (11) carboxylates show two absorption bands i n dioxane. Both bands are analogous to those observed f o r copper (11) acetate monohydrate. This r e s u l t has been explained i n terms of a structual conversion from a poly-meric to a dimeric configuration? 0 i n dioxane. The i n f r a r e d absorption spectrum of dimeric copper (11) 1 11 acetate^ 2 d i f f e r s markedly from that of polymeric copper (11) f o r m a t e d The former shows an anti-symmetric COO" stretching v i b r a t i o n band at ca. 1595 to 1600 cmT1 which i s rather sharp and well-defined, whereas the l a t t e r shows a broad, strong band over the region between 1560 and 1600 cmT1. Tsuchida^ 2 and Kuroda38 found that many dimeric copper (11) n-alkanoates have the same band at 1595 to 1600 cm!1 as observed f o r copper (11) acetate monohydrate. They believed the presence of a sharp band i n t h i s region to be further evidence f o r a binuclear configuration,, Kuroda37s39 also found that the a n t i -symmetric COO- stretching frequencies of copper (11) £>{,LJ-carbo-xylates, ( with the exception of copper (11) malonate ),. Cu(CH2)n-2( C 0°)2 (n=2-10), which have subnormal magnetic moments ( ;u = 1.20 - 1.45 B.M. ) s h i f t to higher frequencies with respect to the bands of the corresponding sodium salts« Kuroda also measured the i n f r a r e d absorption spectra of copper (11) formate i n the c r y s t a l l i n e state and i n dioxane and found that the a n t i -symmetric COO" stretching v i b r a t i o n i s higher i n the l a t t e r case where the copper (11) s a l t i s dimeric. The aim of the present work was to investigate further the adducts of copper (11) aryl-carboxylates with organic bases. The work mainly concerns the pyridine adducts of copper (11) benzoate and copper (11) ortho-„ meta- and para-chlorobenzoate. I t should be mentioned here that when t h i s work was i n i t i a t e d there were no r e s u l t s reported i n the l i t e r a t u r e on the adducts of copper (11) aryl-carboxylates but during the l a s t two years there have been several publications i n t h i s f i e l d . For the 12 most part the work of other authors has supplemented our own. This f a c t w i l l be made clea r i n the discussion section of t h i s thesis. In addition no de t a i l e d study has been reported on the basic s a l t s of copper (11) carboxylates. Such a study was made i n the present work on the basic s a l t s of copper (11) benzoate and the three chloro d e r i v a t i v e s . 13 Chapter I I . Experimental 2 - 1 . Preparation of Copper (11) Complexes. As has been mentioned i n the l i t e r a t u r e 2 ^ , using various procedures and s t a r t i n g materials i n the preparation of copper (11) carboxylates may r e s u l t i n the formation of d i f f e r e n t modifications of the same compound. Consequently, d e t a i l s of the preparation of a l l compounds, including those which have been reported i n the l i t e r a t u r e , w i l l be given here. A n a l y t i c a l data are given i n Table I. Table I . Analyti c a l data. Compound m.p.(°C) (dec.) Color Analysi s % C i (Theoretical) % H % Cu Cu(C^H^C0 2) 2 280-282 blue 55.13 v (54.49) 3.28 (3.3 ) 20.68 (20.78) Cu(o-C1C 0H>C0 2) 2 254.5-256 green ' 45.09 (44.88) 2.07 (2.16) 17.00 (16.94) Cu(m-ClCoHZ}.C02)2 262-263 blue 45.21 (44.88) 2.92 (2.16) 16.98 (16.94) Cu(p-C1C6H4C02)2 287-289 blue 44 . 7 9 (44.88) 2.65 (2.16) 16.85 (16.94) Cu(0H)(C6H5C02) 257-259 pale blue 41.88 (41.69) 3.21 ( 3 . - ) 31.^9 (31.5D Cu(OH)(0-CIC6H4CO2) 184-184.5 pale blue 35.61 (35.60) 2.24 (2.16) 27.00 (26.88) Cu(0H)(m-ClC6H4C02) 253-255 . pale blue 35.46 (35.60) 2.26 (2.16) 26.95 (26.88) Cu(0H)(p-ClC6R>C02) 251-253 pale blue 35.96 (35.60) 2.49 (2.16) 26.81 (26.88) ( continue on next page ) 14 ( continue on Table I ) Compound m.p.(°Q) (dec.) Analysis (Theoretical) Color JH ^~Cu Cu(m-ClC/;Hj!,C02)2' 246-248 blue 46.69 3-77 13 .60 (dioxane 7 (46.65) ( 3 - ^ 6 ) (13 .72) C u ( C 6 H 5 C 0 2 ) 2 ' 239-241 blue 60.07 4 . 4 3 13.18 6 . 3 8 2 p y r i d i n e « H 2 0 (60 . 0 0 ) ( 4 . 6 0 ) ( I 3 . I 8 ) (5.80) Cu(o-C1C$H>C02)2" 2 0 5 - 2 0 6 blue 5 4 . 0 1 3 . 2 6 11.64 5 . 2 7 2 p y r i d i n e ( 5 ^ . 0 8 ) (3.4o) ( 1 1 . 9 2 ) ( 5 . 2 6 ) Cu(m-ClCgH4Ce2)2' 224-225 blue 5 4 . 4 4 3 . 8 3 1 1 . 9 5 5 . 0 8 2 p y r i d i n e ( 5 ^ . 0 8 ) (3.40) ( 1 1 . 9 2 ) ( 5 . 2 6 ) Cu(p-C1C6H4C02)2* 2 2 7 - 2 2 9 blue 5 4 . 7 3 3 . 9 2 11.66 5 . 2 1 ^pyridine ( 5 ^ . 0 8 ) ( 3 . ^ 0 ) ( 1 1 . 9 2 ) ( 5 . 2 6 ) Cu ( C 6 H 5 C 0 2 ) 2 * 2 3 6 - 2 3 7 green 5 9 . 5 8 3 . 8 0 1 6 . 4 9 3 . 8 8 pyridine ( 5 9 . 2 9 ) (3.93) ( 1 6 . 5 D (3.64) Cutm-ClC^a^^* 224-225 green 51 .01 3 . 4 4 I 3 . 7 0 2.64 pyridine ( 5 0 . 2 3 ) ( 2 . 8 9 ) (13-99) ( 3 . 0 9 ) Cufp-ClColIiLC^^ 2 3 0 - 2 3 2 green 5 I . 5 6 2 . 8 6 13 .89 3 . 3 8 -pyridine ( 5 0 . 2 3 ) ( 2 . 8 9 ) ( 1 3 . 9 9 ) ( 3 . 0 9 ) Cu(p-C1C6H4C02)2* 248-249 green 48.41 3.42 1 5 . 3 8 1.61 " I p y r i d i n e ( 4 7 . 7 8 ) (2 .55) (15.33) (I.69) 15 2-1-1. Aryl-Carboxylates. Copper (11) benzoate 22,25*30,42 . "Chemical reagent grade" benzoic acid (10 g.) suspended i n water (20 ml.) was neu t r a l i s e d with 0.1 N. aqueous sodium hydroxide solution u n t i l a pH. value of 7.6 was observed. When thi s solution was slowly added with s t i r r i n g to an aqueous (100 ml.) solution of copper (11) s u l f a t e pentahydrate (16 g.), a pale blue p r e c i p i t a t e formed. The p r e c i p i t a t e was f i l t e r e d and washed repeatedly with water. Wash-ing was continued u n t i l neither the f i l t r a t e nor the p r e c i p i t a t e gave a p o s i t i v e reaction f o r sul f a t e i on. The product was r e c r y s t a l l i s e d from acetone, y i e l d i n g a blue p r e c i p i t a t e which was heated to constant weight i n a drying p i s t o l at 111 °C / 10 mm. Hg.. Copper (11) ortho-chlorobenzoate5^»70 • This compound was prepared as described above, using copper (11) s u l f a t e penta-hydrate and ortho-chlorobenzoic a c i d as s t a r t i n g materials. The green c r y s t a l s obtained were r e c r y s t a l l i s e d from acetone and dried i n the a i r at room temperature. Copper (11) meta-chlorobenzoate7Q % Pale blue copper (11) meta-chlorobenzoate was obtained from copper (11) s u l f a t e penta-hydrate and meta-ohlorobenzolc a c i d following the procedure described f o r copper (11) benzoate. The compound was dried i n an oven at 50°C. and was r e c r y s t a l l i s e d from p-dioxane and dried again i n a drying p i s t o l at 111 °C / 10 mm. Hg.. 16 Copper (11) para-chlorobenzoate? 0 : Following the same procedure as outlined above f o r the preparation of the meta-chloro deri v a t i v e , copper (11) para-chlorobenzoate was obtained as blue c r y s t a l s . 2-1-2. Basic Salts of Aryl-Carboxylates. Basic s a l t s of copper (11) benzoate^ 0, copper (11) ortho-. meta-, and para-chlorobenzoate were prepared according to the following method. Water was added to a b o i l i n g solution of the normal s a l t ( 3 g.) i n acetone, r e s u l t i n g i n the p r e c i p i t a t i o n of a pale blue product. Addition of water was continued u n t i l p r e c i p i t a t i o n ceased and the suspension was refluxed f o r several hours. The p r e c i p i t a t e was then f i l t e r e d off and washed tho-roughly with several portions of warm acetone. A l l four basic s a l t s were found to be insoluble i n acetone, benzene, d i e t h y l ether, ethanol, ethyl acetate, ethylene g l y c o l , methanol, tetrahydrofuran and water. They dissolved with decomposition i n pyridine. 2-1-3. Dioxane and Pyridine Adducts of Aryl-Carboxylates. Copper (11) meta-chlorobenzoate mono-p-dioxane : Anhydrous copper (11) meta-chlorobenzoate (1 g.) was dissolved In b o i l i n g p-dioxane (100ml.) . The deep blue solution was f i l t e r e d hot and on cooling to room temperature the mono-dioxane deriv a t i v e p r e c i p i t a t e d . The c r y s t a l s were washed with p-dioxane and dr i e d i n a des.sj£cator over calcium chloride. 17 Copper; (11) benzoate dlpyrldine monohydrate^5 : Copper (11) benzoate (1 g.) dissolved i n the b o i l i n g mixed-solvent, acetone (80 ml.) - water (10 ml.) - pyridine (5 ml.), gave a blue solution which on evaporation at room temperature yielded a blue p r e c i p i -tate. The product was ground in t o a f i n e powder, washed with acetone containing pyridine and allowed to dry i n the atmos-phere at room temperature. Dlpyrldine adducts of copper (11) ortho-, meta- and para-chlorobenzoate : Anhydrous copper (11) ortho-chlorobenzoate (1 g.) was dissolved i n b o i l i n g pyridine ( 25 ml. ), y i e l d i n g a blue solution which was f i l t e r e d hot and allowed to cool to room temperature. The bright blue p r e c i p i t a t e which formed immediately on cooling was recovered and dried i n a dessicator over calcium chloride. The dlpyrldine adducts of copper (11) meta- and para-chlorobenzoate were obtained by analogous proce-dures. 42 6 5 Copper (11) benzoate monopyridine : ' D Copper (11) benzoate dlpyrldine monohydrate (1 g.) was dried i n a vacuum dessicator (10 mm. / Hg.) over s u l f u r i c acid f o r seven days. Copper (11) meta-chlorobenzoate monopyridine : This com-pound was prepared from copper (11) meta-chlorobenzoate dlpy-r l d i n e by a procedure analogous to that described above f o r the preparation of copper (11) benzoate monopyridine. Monopyridine and hemlpyrldlne adducts of copper (11) para-chlorobenzoate : Attempts to transform the dipyridine 18 adduct of copper (11) para-chlorobenzoate into i t s monopyridine derivative by a procedure analogous to that described above f o r the preparation of copper (11) meta-chlorobenzoate monopyridine were unsuccessful. When the dipyridine adduct of copper (11) para-chloroben-zoate i s heated under reduced pressure (10 mm. / Hg.) pyridine i s l o s t , the composition of the residue being determined by the size of sample, period of heating and the temperature. Some res u l t s obtained on a 800 mg. sample of the dipyridine adduct are given below. Temperature <°C) Period of Copper heating content (hrs.) ( % ) 65 5 12'. 82 77 9.5 12.60 77 10 13.^3 77 12.5 13.89 77 14 14.82 77 16 14.83 77 21 14.85 80 14.36 111 10 15.38 Hence i t was possible to obtain a sample of composition very close to Cu(0C0C5Hij-Cl)2'pyridine by heating 800 mg. of the dipyridine adduct at 77°C f o r 12.5 hours. This sample i s referred to as the monopyridine adduct of copper (11) para-chlorobenzoate throughout t h i s t h e s i s . S i m i l a r l y the substance referred to i n t h i s thesis as the hemipyridine adduct of 19 copper (11) para-chlorobenzoate was obtained by heating 800 mg. of the dipyridine adduct at 111°C f o r 10 hours. 2-2. Preparation of Sodium Aryl-Carboxylates. Sodium ortho-. meta- and para- chlorobenzoate and sodium benzoate were prepared by d i s s o l v i n g the corresponding carbo-x y l i c acids i n 0.04 N. sodium hydroxide solu t i o n u n t i l the r e s u l t i n g solutions had pH values of 8 . 0 , 8.4, 8 .53 and 8.59 respectively. The solutions, evaporated to dryness i n an oven at 60 °C, yielded c o l o r l e s s s a l t s which were dried at 1110C. 2-3. P u r i f i c a t i o n of Solvents. M Eastman Kodak n reagent grade jp-dioxane was dried over sodium and then d i s t i l l e d . " Eastman Kodak M reagent grade pyridine was d r i e d over potassium hydroxide p e l l e t s f o r several days and d i s t i l l e d before use. Reagent grade acetone was used without further p u r i f i c a t i o n . 2-4. Analyses. Elemental analyses were obtained f o r a l l compounds studied. Copper was determined iodometrically using 0.01 molar sodium th i o s u l f a t e s o l u t i o n ^ . Carbon, hydrogen and nitrogen analyses were obtained i n the mlcroanalytical laboratory of t h i s Depart-ment. 2-5. Magnetic S u s c e p t i b i l i t y Measurements. 20 Magnetic s u s c e p t i b i l i t y measurements employing the Gouy method were made using two separate apparatus. The one, employing a microbalance and a permanent magnet ( ca. 7000 Gauss with a 13 mm. pole gap ), was used i n the determination of the room- temperature magnetic s u s c e p t i b i l i t i e s . For a l l compounds studied the re s u l t s reported are the average of at l e a s t three separate determinations ( each involving repacking of the Gouy tube ). The other Gouy apparatus equipped with an electromagnet and a semimicrobalance, has been described i n the l i t e r a t u r e ? . This apparatus with a f i e l d strength of ca. 7800 Gauss was used to measure the temperature dependence of the magnetic s u s c e p t i b i l i t i e s over the temperature range from 330 to 87°K. Magnetic s u s c e p t i b i l i t i e s f o r a l l compounds were also tested f o r f i e l d dependence using the l a t t e r appa-ratus at four d i f f e r e n t f i e l d strengths ( 4000, 5900, 7800 and 9300 Gauss ). For a l l compounds studied i n t h i s work, the magnetic s u s c e p t i b i l i t y was found to be f i e l d independent at room temperature. The Gouy tube was made of 4 mm. inner diameter pyrex glass tube. C a l i b r a t i o n was achieved with a gr a v i m e t r i c a l l y analysed Nickel ( l l ) chloride s o l u t i o n ^ 2 . The room-temperature moments were calculated from the s u s c e p t i b i l i t y and , the temperature independent contribution to the paramagnetism per gram-ion of copper. A value of where OCm i s the molar 21 No< = 60 x 10~6 emu.13 was used i n the c a l c u l a t i o n of the mag-ne t i c moments f o r a l l compounds. The diamagnetic corrections f o r the copper atom and the ligands were estimated from data given by Lewis* 2, Selwood57. and Foexl5. 2-6. Diffuse Reflectance Spectra. Diffuse reflectance spectra were measured at room tempe-rature on a Cary 14 reflectance spectrophotometer, using mag-nesium carbonate U.S.P. as the reflectance standard. The pow-dered samples were pressed between s i l i c a - g l a s s p l a t e s . 2-7. Infra-red Absorption Spectra. Infra-red absorption spectra of the s o l i d s a l t s were.exa-mined as mulls i n Nujol and i n hexachlorobutadiene and were recorded on a Perkin-Elmer model I37 KBr spectrophotometer and model 137 NaCl spectrophotometer. A f i l m of polystyrene was used to c a l i b r a t e the NaCl region. 22 Chapter I I I . Results and Discussion 3-1. Magnetic S u s c e p t i b i l i t y Studies. 3-1-1 Copper (11) Aryl-Carboxylates and t h e i r Monopyridine and Monodioxane Adducts. I t i s apparent from the data given i n Table II that a l l these compounds show subnormal room-temperature moments of 1.32 - 1.45 B.M. i n good agreement with p. = I.30 - 1.49 B.M. found f o r most dimeric copper (11) alkyl- and aryl-carboxylates 2^. This suggests that a l l the aryl-carboxylates of copper (11) and t h e i r monopyridine and monodioxane adducts studied i n t h i s work have dimeric structures, a conclusion supported by the magnetic s u s c e p t i b i l i t y - temperature v a r i a t i o n studies. The OCm - T curves f o r a l l compounds ( with the exception of copper (11) para-chlorobenzoate ) show that the s u s c e p t i b i l i t y increases as the temperature decreases from ca. 330°K and reaches a maximum around room temperature, afterwhich, the s u s c e p t i b i l i t y decreases with decreasing temperature. Following the procedure of Bleaney and Bowers? and Figgis et a l . 1 ^ the observed spin i n t e r a c t i o n s i n dimeric copper (11) s a l t s may be interpreted i n terms of a temperature - dependent equilibrium between a paramagnetic excited state (s =1) and a diamagnetic ground state (s = 0 ) . 2 2 lO^Xm = + l e ^ ( j L ) } - 1 + I where g i s the Lande spectroscopic s p l i t t i n g f a c t o r - ; 23 N, Avogadro9s number ; ^ 9 the Bohr magneton j k, the Boltsman constant j J, the exchange coupling constant ; T, the absolute temperature ; and Ng, i s the temperature-independent paramagnetic contribution to the molar susceptibility of copper (11) In the present study attempts were made to f i t the experi-mental results to the theoretical calculated curves using equat-ion I. Both J and g-values were obtained from equation I by following the same method as described by Figgis et a l . . The calculated equations for the magnetic susceptibility are shown below and given graphically i n Figs. 1-8. Cu ( C 6 H 5 C 0 2 ) 2 Cu(m-C1C5H^C02)2 Cu( 05115002)2' pyridine Cutm-CIC^H" 4 . 0 0 2 ) 2 ' ~" pyridine CU(P-C1C5HILC0 2 )2' "" pyridine Cu(p-ClC5HZj,C02)2' -§pyridine CuCm-ClCgHiiX^^" dioxane l06Xm 106Xm 106Xm 106Xm 106Xm 106Xm 106Xm 0.573/ 1 ^70 1^1 * exp( T 0.559/ 1 + 3 T 1 464 —exp( 3 T f 1 448 [ l + _ e x p ( 3 T ( 1 370 [1 + exp( 3 T 1 3^7 —exp( 3 T 1 3^2 I 1 + exp( T 3 T 0.593/ 1 ^74 1 1 + •—exp( T 3 T T 0.602 T 0.55^ T 0.562 r . [1 + T o . 5 i 9 r -1 + 60 -1 + 60 -1 + 60 -1 + 60 -1 + 60 -1 + 60 -1 + 60 zk Pigs. 1-8 also contain plots of u versus temperature f o r the compounds studied. The moments decrease with decreasing temperature, i n agreement with the presence of strong a n t i f e -rromagnetic i n t e r a c t i o n s . The agreement between the experimental and the t h e o r e t i c a l curves i s not very s a t i s f a c t o r y i n most cases. The disagree-ment becomes more appreciable i n the lower temperature region ( with the exception of the hemipyridine adduct of copper (11) para-chlorobenzoate which shows good agreement between theory and experiment over the entire temperature range ). The d i s -crepancy i s probably due to the presence of trace amounts of other modifications i n which the magnetic i n t e r a c t i o n i s weak. Some uncertaincy a r i s e s also from the choice of J-values. I t i s also possible that the assumption used i n the derivation of equation I that J remains constant over the entire temperature range i s not adequate. The equilibrium constant f o r the Interconversion ^eq. s i n g l e t t r i p l e t may be calculated from the magnetic data according to the method described by H a t f i e l d , Piper and Klabunde 2^. The s i n g l e t state i s assumed to have a moment of 0.0 B.M. and the t r i p l e t state a moment of 2.90-3.10 B.M.. The l a t t e r value was estimated from peff = g[s(S+l)] i n which g was obtained from equation I ( see also Table III ). Since we have 25 assumed a temperature-independent paramagnetism term, = 60 x 10"^ emu, i n c a l c u l a t i n g the e f f e c t i v e magnetic moments, therefore, t h i s value was subtracted from the molar suscepti-b i l i t i e s before the mole f r a c t i o n s of molecules at each tempe-rature were calculated. A p l o t of l o g K eq against T" 1 y i e l d s a straight l i n e i n a l l cases. These curves were used to estimate and A S ° f o r each compound. The r e s u l t s are given i n Table I I I . Values of AH°calculated f o r the compounds are about 10 % l e s s than those calculated from equation I . The observed A.S° values are also close to ( although below ) the value, 2.2 e.u., calculated from A s ° = B»ln3. Lewis and Mabbs^2 reported that anhydrous copper (11) benzoate has f i v e magnetically d i f f e r e n t modifications a r i s i n g from d i f f e r e n t methods of preparation. The room-temperature moments of these f i v e modifications vary from 1.40 to I .78 B.M.. The 'Xm - T curve f o r the one with p. = 1.40 B.M. i s s i m i l a r to that of copper ( l l ) acetate monohydrate and t h i s modification was considered to have a binuclear structure ; the other modifications apparently are not binuclear complexes. In the present study, anhydrous copper (11) benzoate was found to have a room-temperature moment of 1.33 B.M. which i s the lowest moment yet observed f o r t h i s compound. I t s OCm - T curve i s shown i n F i g . I. The experimental r e s u l t s are i n agreement with the t h e o r e t i c a l l y calculated curve from 340 to 210 °K. The values J = 327 cmT1, and g = 2.14 are close to J = 340 cmT1 26 and g = 2.18 reported f o r the form with p. = 1.40 B.M. by-Lewis and Mabbs^2. Accordingly, i t i s concluded that the compound reported here has a binuclear structure. Copper (11) meta-chlorobenzoate Cu = 1.32 B.M.) prepared i n t h i s work has a room-temperature moment considerably smaller than the value = 1.72 B.M. reported elsewhere^3. I t has been suggested previously that the l a t t e r compound Is polymeric and hence we concluded that the former compound i s another modification of copper (11) meta-chlorobenzoate with a binuclear structure. The OCm - T behavior f o r t h i s compound supports t h i s conclusion ( F i g . 2 ) . The room-temperature moment of copper (11) para-chloro-benzoate was found to be 1.44 B.M. which i s close to the value M = 1.30 - 1.40 B.M. generally observed f o r dimeric copper (11) n-alkanoates. The Xm - T curve, however, does not exhibit a maximum over the temperature range studied. As t h i s compound exhibits properties of both dimeric ( low magnetic su s c e p t i b i -l i t y ) and polymeric ( no maximum i n 'Xm - T curve ) copper (11) carboxylates, we conclude that t h i s compound i s probably a mixture of dimeric and polymeric species. Molecular weight data i s needed f o r t h i s compound. Copper (11) benzoate monopyridine was reported by W i l k i n s o n ^ et a l . to have a room-temperature moment of u = I .30 B.M.. Recently, Lewis and Mabbs^2 i s o l a t e d a new speci-men with p. = 1,42 B.M.. In the present study, a value of 27 p. = I .39 B.M, was found f o r the same compound. The values of two parameters J and g calculated from equation I are 311 cmT* and 2.19, respectively, which are i n good agreement with these reported by Lewis et a l . . Table I I . Room-temperature magnetic data f o r copper (11) aryl-carboxylates and r e l a t e d compounds. Compound3, Temp., 296 n A g , -106A , 106Xm, M e f f(B.M.) Cu( 0 ^ 5 0 0 3 ) 2 2 . 1 2 148 797 1.33 Cu(m-ClC6R"2j.C02)2 294.5 1.65 176 795 1.32 Cu(p-C1C6H£),C02)2 295 2 . 0 2 176 93^ 1.44 Cu ( C 6 H 5 C 0 2)2'Py 297.5 1.74 197 865 1.39 Cutm-ClCgHtyCO^)2*Py 295.5 1.58 225 942 1.45 Cu(p-ClC6H^C02)2*py 295 1.63 225 965 1.45 . Cu(p-ClC5H4C0 2)2'lpy 296 1.80 201 946 1.45 Cu( m- CI C6H2J.CO2) 2 * d i ° x • 296 1.26 233 816 1.35 where "Xg Is the gram s u s c e p t i b i l i t y (e.g. s.;e.m. u.) ; "Xm, the molar s u s c e p t i b i l i t y ( corrected f o r the dlamagnetism of. a l l atoms ) ; A, the molar diamagnetic correction ; a and. py, pyridine ; diox, para-dioxane. 28 Table I I I . Calculated values of g, Tc, J , and AS° f o r ( C u ( X - C 6 H 4 C 0 2 ) 2 - L ] 2 . g Tc(°K) J Kcal * H ° ( — — ) A S (e.u.) cm!1 Kcal mole mole X L X L X L X L X L X L X L 2.14 294 327 0.94 meta-chloro 2.11 290 323 0.92 n i l 2.19 280 2.11 231 H n i l H pyridine meta-chloro pyridine para-chloro 2.12 217 pyridine para-chloro 2.04 214 hemipyridine meta-chloro 2.18 296 dioxane 311 0.89 257 0.74 241 O.69 238 0.68 328 0.94 0.81 0.81 0.75 O.63 0.58 0.71 O.83 1.7 1.9 1.7 1.8 1.8 2.3 1.8 29 Table IV. Experimental gram and molar s u s c e p t i b i l i t i e s , (e.g.s.,e.m.u.), magnetic moments (B . M . ) and equilibrium constants f o r the s i n g l e t - t r i p l e t interconverslon f o r anhydrous copper (11) aryl-carboxylates and re l a t e d compounds. Copper (11) benzoate Temp.(°K) 10 6Xg lo6xm Meff(B.M.) K e q . 333.7 2.07 781 1.39 0.725 321 2.08 785 ' 1.37 0.685 307.5 2.09 788 1.35 0.642 296 2.12 797 1.33 0.616 283.3 2.10 791 1.30 0.567 269 2.06 778 1.25 0.509 253 2.05 775 1.21 0.462 232.8 1.99 757 1.14 0.396 217 1.91 733 1.08 0.3^3 196.3 1.77 690 1.00 O.276 181 I.69 665 0.941 0.237 161 1.48 601 0.838 0.215 148.3 1.34 558 0.772 0.148 128.3 1.05 469 O.650 0.101 112.9 0.847 407 0.564 0.0735 106 0.793 391 0.532 O.O653 87 0.642 344 0.446 0.0451 Copper (11) meta-chlorobenzoate 378 1.51 742 1.44 0.882 363 1.52 746 1.42 0.828 346 1.56 761 1.40 0.789 335 1.58 769 1.39 O.760 317 1.59 772 1.35 O.696 298 I.63 787 1.32 O.650 294 I.63 787 1.31 O.636 281 I.63 787 1.28 0.591 260 1.61 780 1.23 0.516 249 1.60 776 1.20 0.480 239 1.61 780 1.18 0.455 221 1.60 776 1.13 0.404 203 1.57 765 1.07 0.352 185 1.45 720 0.992 0.285 I67 I.27 652 0.892 0.219 148 1.08 581 0.789 O.I63 128 0.775 467 0.648 0.105 107 0.559 386 0.530 0.0677 88 0.459 348 0.451 0.0483 30 ( continue on Table IV ) Temp.(°K) 10 6Xg l0 6Xm. » e f f(B.M.) 1.51 1.54 1.51 1.50 1.49 1.45 1.43 1.40 1.36 1.33 1.29 1.26 1.22 1.19 1.18 1.09 1.04 0.980 0.947 Copper ( 1 1 ) para-390 1.62 7 8 4 376 1.77 840 361 1.78 844 3 4 3 I.87 8 7 7 328 1.91 8 9 2 3 0 7 . 5 1.96 9 1 1 2 9 3 1.99 9 2 2 281 1.99 9 2 2 2 6 1 2.04 941 2 4 5 2 . 0 7 9 5 2 2 2 7 2.11 9 6 7 2 1 2 2 . 1 7 9 9 0 1 9 7 2 . 1 9 9 9 7 182 2 . 2 6 1024 1 6 2 2 . 3 4 1 0 5 4 146 2.40 1 0 7 6 128 2 . 4 5 1 0 9 5 1 1 2 . 2 . 5 2 1 1 2 1 9 7 2 . 7 5 1 2 0 7 3 3 5 3 2 3 . 5 310.7 301 2 9 6 2 8 0 . 5 264.3 247.2 2 3 6 . 7 2 1 9 . 3 198.5 176.7 161.6 144 1 2 3 108 9 2 Keq. Copper ( 1 1 ) benzoate monopyridine 1.71 8 5 5 1.47 0 . 8 1 3 1.72 8 5 9 1.45 0 . 7 7 ° 1.74 8 6 7 1.42 0 . 7 3 ° 1 . 74 8 6 7 1.40 0 . 6 9 2 1 . 7 4 8 6 7 1.39 0 . 6 7 3 1 . 7 5 871 1.35 0 . 6 2 1 1 . 7 3 8 6 3 1.31 0 . 5 5 6 1.74 8 6 7 1.27 0 . 5 ° 6 1.71 8 5 5 1 . 2 3 0.464 I.67 840. 1.17 0 . 4 0 5 I.63 8 2 5 1.11 0 . 3 4 3 1.47 7 6 3 1.00 0 . 2 6 4 1.39 7 3 2 0 . 9 3 7 0.224 1.22 6 6 7 0.840 0 . 1 7 3 1.00 5 8 2 0 o 7 2 1 0 . 1 2 1 0 . 7 7 6 4 9 6 0 . 6 1 6 0 . 0 8 6 1 O.665 4 5 3 0.540 0 . 0 6 4 8 31 ( continue on Table IV ) Temp.(°K) i c A g l06<Xm ;ueff.(B.M.) K e q. Copper (11) meta-chlorobenzoate monopyridine 322.4 1.46 888 1.47 O.938 309.2 I.50 906 1.46 0.902 300.2 I.58 942 1.46 0.924 295.5 1.58 942 ' 1.45 0.896 283 1.59 947 1.42 0.835 265.7 1.61 956 1.39 0.760 248 1.62 96I . I.34 0.681 231 I.63 965 1.30 0.610 212.5 I.63 965 1.24 0.535 19^.5 1.59 9^7 1.18 0.455 177 1.55 929 1,11 0.387 157.7 1.49 902 1.04 0.317 140 1.47 892 0.972 0.268 121 1.44 879 0.897 0.219 105 1.3^ 833 0.808 0.173 88 I.23 783 0.716 0.130 Copper (11) para-chlorobenzoate monopyridine 324 312 300 288 272 255.2 236.4 217.7 198.2 178.6 158.4 140 123 104 85 1.53 920 1.50 0.999 1.58 942 1.49 0.975 1.60 951 1.47 0.921 1.64 970 1.45 0.887 I.67 983 1.42 0.819 1.72 1006 . 1.40 0.764 1.75 1020 1.35 0.687 1.79 1038 1.31 0.618 1.77 1029 1.24 0.525 1.75 . 1020 1.18 0.444 1.74 1015 1.10 0.372 1.71 1001 1.03 0.309 1.68 988 0.959 0.258 1.81 1047 0.9H 0.226 2.04 1151 0.865 0.199 -J 32 ( continue on Table IV ) Temp.CK) 10 6Xg l0 6Xm ;u e f f >(B.M.) K e q > 33^.7 321.4 311.7 300.5 284.6 272.3 259 244.7 230 213.6 197 181 I 6 3 146.6 128 108.3 89 Copper (11) para-chlorobenzoate hemipyridine 1.73 917 1.52 1.75 926 1.50 1.78 938 1.49 1.78 938 1.46 1.81 950 1.43 0.949 1.80 . 946 1.39 0.866 1.80 946 1.36 0.790 1.78 938 1.32 0.704 1.85 967 1.30 0.667 1.87 975 1.25 0.602 1.85 967 1.20 0.524 1.79 942 1.14 0.443 I.69 901 1.05 0.358 1.52 830 0.955 0.277 1.34 756 0.847 0.207 1.05 636 0.710 O.I36 0.633 463 0.538 0.0741 319 311 301 296.3 285 274 259 245 227 210 191 174 151 127 107 88 Copper (11) meta-•chlorobenzoate monodi oxane 1.22 798 1.38 0.667 1.25 812 1.38 0.659 1.25 812 1.35 0.625 1.26 816 1.35 0.615 1.24 808 1.31 0.568 1.25 812 1.29 0.539 1.22 798 1.24 0.481 1.21 794 1.21 0.440 1.17 765 1.14 0.374 1.11 747 1.08 0.325 1.05 • 719 1.01 0.272 0.954 675 0.93° 0.222 0.744 577 0.794 0.153 0.588 505 0.675 0.106 O.386 •412 0.551 0.0684 0.208 329 0.437 0.0419 3 33 Temp. (°K) F i g . I . Cryomagnetic data f o r copper (11) benzoate. 3 V 900 700 500 o •rH 300 100 1.5-l . o -so m CD ct-H* o 0 o B . CO ct s 0 Experimental s u s c e p t i b i l i t y ^ Calculated from equn. I Experimental moment, Aeff9 106Xm 0.1-ldo POO 300 Temp. (°K) F i g . 2 . Cryomagnetic data f o r copper (11) meta-chlorobenzoate. 35 .6 120,0 2.0-"1100 (J) Tooo ^ S s . ^ - ^  1.5-' 900 ^ ^ S L 1 » " \ V / " 800 / ^ y \ y \ — 0 Experimental s u s c e p t i b i l i t y Calculated from equn. I — Experimental moment, ;u eff m 1 , . . 1 l . \ 100 200 30 Temp. (°K) F i g . 3. Cryomagnetic data f o r copper (11) para-chlorobenzoat e. 36 900 700 500 300 100 0 Experimental s u s c e p t i b i l i t y , — Calculated from equn. I 0 . 5 -— Experimental moment, nefft TOTT "20 CT ct B o 0 CD ct td lO^Xm Temp. (°K) Fi g . 4. Cryomagnetic data f o r copper (11) benzoate monopyridine. 37 100 200 300 Temp. (°K) F i g . 5. Cryomagnetic data f o r copper (11) meta-chlorobenzoate monopyridine. 38 Temp. (°K) F i g . 6. Cryomagnetic data f o r copper (11) para-chlorobenzoate monopyridine. 39 100 200 300 Temp. (*K) F i g . 7. Cryomagnetic data f o r copper (11) para-chlorobenzoate hemipyridine. 40 Temp. T K ) F i g . 8. Cryomagnetic data f o r copper (11) meta-chlorobenzoate mono-p-dioxane. 41 3-1-2. Dipyridine Adducts of Copper (11) Aryl-Carboxylates. As can be seen c l e a r l y from Table V copper (11) benzoate dipyridine monohydrate shows a room-temperature moment of 1.85 B.M.j which i s s l i g h t l y smaller than that ( p. = 1.90 B.M. ) reported by Wilkinson^5 et a l . . This discrepancy between the two r e s u l t s i s perhaps caused by adap^.ng a temperature indepen-dent paramagnetism term, N^ = 60 x 10" ^ emu. i n the present study. Since no d e t a i l e d cryomagnetic data was given by these authors no further comparison of r e s u l t s may be made. The res t of the copper (11) complexes i n Table V also show room-tempera-ture moments comparable to the values ( ;u = 1.80-2.00 B.M. )*2» ^1»57 generally observed f o r magnetically d i l u t e copper (11) complexes and i n d i c a t i n g absence or at most only weak metal to metal i n t e r a c t i o n i n these carboxylate complexes. Results of cryomagnetic studies of these complexes over the temperature range 90-330°K are given i n Table VI. The compounds obey the Curie-Weiss law. C QCm = 2 T - 9 Values of the Weiss constant, 0, are given i n Table V. Since the Weiss constants f o r a l l four dipyridine complexes are small, magnetic i n t e r a c t i o n must be r e l a t i v e l y weak i n these compounds. I t should be mentioned that deviation from the Curie-Weiss law was observed below 170°K f o r copper (11) ortho-chlorobenzoate d i p y r i d i n e . No reasonable explanation f o r t h i s deviation i s possible at present. I t i s possible that the dipyridine adducts have monomelic structures with the carboxylate groups acting as chelating ligands. However as M a r t i n i pointed out the.formation of a four membered chelate r i n g i s s t r u c t u a l l y unfavorable and as a r e s u l t a polymeric structure In which each carboxylate group forms a bridge between two copper atoms seems more favorable. Moreover, our r e s u l t s on these compounds suggest the presence of weak antiferromagnetic i n t e r a c t i o n s which could occur v i a the bridging carboxylate groups and hence support polymeric structures f o r these compounds. A suggested possible structure f o r these dipyridine adducts i s shown i n F i g . 9. Each copper atom i s s i x coordinate with four short and two long bonds. The four shorter bonds being formed to two pyridine molecules and two carboxylate groups with two a d d i t i o n a l carboxylate groups forming the two longer bonds. F i g . .9. Proposed polynuclear structures f o r the d i -pyridine adducts of copper (11) aryl-carbo-xylates. *3 From the s i m i l a r i t y i n i t s magnetic properties with the analogous chloro derivatives,, the di p y r i d i n e monohydrate adduct of copper (11) benzoate may also be a polynuclear complex,. However, i t i s not easy to speculate on a d e t a i l e d structure f o r t h i s compound since the p o s s i b i l i t y e xists that the water molecule may also bridge copper atoms as i n copper (11) benzoate t r i h y d r a t e 2 ^ . In summary, our r e s u l t s i n the magnetic properties of pyridine compounds ind i c a t e that coordination of one molecule of pyridine per copper atom i n binuclear copper (11) carboxylates r e s u l t s i n no basic change i n the structure 5 the molecule of pyridine simply occupies the terminal p o s i t i o n as water,does i n the copper (11) acetate monohydrate structure. Coordination of a second molecule of pyridine per copper atom, however, re s u l t s i n a breakdown of the binuclear structure and the formation of a polymeric structure. Table V. Room-temperature magnetic data f o r d i p y r i d i n e adducts of copper (11) aryl-carboxylates. b Compounds Temp., 106%E,- -10 6^, l0 6Xm, -^eff, B« M» Weiss const. (°K) Cu(C 6H 5C0 2) 2«2py.H 20 295 2.58 259 . 1503 1.85 - 7 . 3 Cu(o-ClC 6H 4C0 2) 2»2py 296 2.07 274 1377 1.77 -27.5 Cutm-ClCgH^CC^) 2° 2py 296.5 2.24 274 1468 1.84 -14.6 Cu(p-ClC5H4C0 2) 2°2py 295 2.21 274 1452 1.82 -10.0 b ; py, pyridine 4 5 Table VI. Experimental gram and molar s u s c e p t i b i l i t i e s (c.g.s.,e.m.u.) and magnetic moments (B.M.) f o r dipyridine adducts of copper (11) a r y l -carboxylates. Cu(C^H^COg) 2•2pyri di ne•H 20 Temp.(cK) l O ^ g lO^Xm >u e f f # (B.M.) 297.2 2.58 1503 1.86 290.6 2.59 1507 1.85 283.3 2.67 1546 1.85 269.6' 2.80 1609 1.84 254 3.02 1715 1.84 236.7 3.26 18 30 1.84 218.6 3*56 1975 1.84 200.5 4.15 2259 1.89 180.7 4.60 2476 1.88 159 5.16 2746 1.85 144.5 5.62 2968 1.84 126.6 6.43 3358 1.84 107 7.45 3850 1.81 92 8.62 4414 1.80 Cu(o-ClC 6H^C0 2)2* 2 p y f i d i n e 305 1.89 1281 1.74 301 2.02 1351 1.77 296 2.07 1377 1.77 277 2.18 1436 1.76 264 2.31 1505 1.76 250 2.45 1580 1.75 243 2.53 1623 1.75 222 2.71 1718 1.73 207 2.90 1820 1.72 191 3.24 2001 1.73 174 3»59 2188 1.73 156 3.91 2358 1.70 140 4.64 2747 1.74 125 5«31 3104 1.75 109 6.00 3^72 1.73 86 7.60 4325 1.72 46 ( continue on Table VI ) Temp.rK) 10 ^Xg lO^m ^ e f f . ( B , M , > Cu(m-ClC5H4C0 2)2'2pyridine 296.5 2.24 1468 1,84 283,2 2 ,30 1500 1.82 267 2.47 1591 1.82 249.2 2.67 1697 1.82 231.7 2 .85 1793 1 .80 212.1 3,13 1942 1.79 191 .3 3.50 2140 1.79 169 .3 4,17 2497 1.82 149.6 4 ,73 2795 1.81 130.8 5.38 3142 1.80 113.2 5.64 3280 I . 7 2 98.2 7.08 4048 1.78 Cu(p-ClC 6H^C0 2 ) 2 ° 2 p y r i d i n e 295 2.21 1452 1.82 287.5 2.28 1489 1.82 275.6 2.38 1543 1.80 259.5 2.55 1633 1.80 241.5 2,80 1766 1.82 224.5 3.01 1878 1.81 205.6 3.32 2044 1.81 187 .4 3.65 2219 1.81 165.5 4 ,35 2593 1.84 151.5 « 4 .75 2806 I . 8 3 I36.I 5 . 2 9 3094 1.83 117.3 5 . 9 7 3^56 1.79 105.9 6,47 3723 1.77 91.1 7.76 4410 1.79 ^7 9.00 7.00 5.oo 3.00 A B c D Experimental r e c i p r o c a l s u s c e p t i b i l i t y , 10- 2Xm"l Cu(C 5H5CO 2 ) 2 • 2 p y • H 2 0 Cu(o-cic^H^cog)2' 2py C u ( m - C l C 5 H ^ C 0 2 ) 2 • 2 p y C u ( p - C l C 6 H ^ C 0 2 ) 2 • 2 p y F i g . 1 0 , 2 0 0 Temp. (°K) Cryomagnetic data f o r the dipy r i d i n e adducts of copper ( 1 1 ) aryl-carboxylates, 48 3-1-3- Basic Salts of Copper (11) Aryl-Carboxylates. The room-temperature moments of a l l four basic s a l t s of copper (11) aryl-carboxylates (Table VII) are normal. Plots of the inverse s u s c e p t i b i l i t y against temperature y i e l d straight l i n e s i n conformity to the Curie-Weiss law with small p o s i t i v e Weiss constants f o r the basic s a l t s of copper (11) benzoate and copper (11) para-chlorobenzoate ? and negative constants f o r the basic s a l t s of copper (11) ortho- and meta-chlorobenzoate. Deviation from the law occurs at 150, 140 and 170°K f o r the ortho-. meta- and para-chlorobenzoate of copper (11), respectively. The d e t a i l e d data f o r the calculated magnetic moments and the values of the Weiss constants are shown i n Tables VII-VIII. The appearance of the Weiss constants Indicates again as i n the dipyridine complexes of the normal s a l t s an add i t i o n a l term which contributes to the t o t a l s u s c e p t i b i l i t y ( which may ari s e from weak metal-metal Interaction i n these compounds ). Unlike the normal s a l t s of copper (11) carboxylates and t h e i r adducts with either pyridine or dioxane, the basic s a l t s display a remarkable i n s o l u b i l i t y i n polar and non-polar solvents. Thus, both magnetic and solvent properties indicate that the basic s a l t s are polynuclear complexes. The p o s s i b i l i t y exists that i n these compounds both the hydroxyl and carboxylate groups are bridging ligands forming i n f i n i t e chains as shown i n 49 F i g . 11. Oxygen atoms from carboxylate groups i n chains above and below the one shown i n the figu r e could complete a d i s t o r t e d octahedral coordination about each copper atom. C 6 H 5 h C 6 H 5 Cu ^ Cu / Cu Cu / o ^ V o x x l x c ' i H I H C6H 5 F i g . 11. Proposed structure f o r the basic s a l t s of copper (11) aryl-carboxylates. 50 Table VII. Room-temperature magnetic data f o r basic s a l t s of copper (11) a r y l -carboxylates. Compounds Temp., lO^Xg, - 1 0 ^ , lO^Xm, ;u B.M., Weiss (°K) e i r . const. <°K) Cu(0H)(C 6H 5C0 2) 295.5 7.60 88 1623 1.93 2.7 Cu(OH)(o-ClC 6E^C0 2) 293.5 5.66 102 1^38 1.80 -18 .5 Cu(OH)(m-ClC6H^C02) 293.5 6.21 102 I568 . I .89 -23.9 Cu(0H)(p-ClC6Hi J.C02) 296 7.26 102 1815 2.05 8.1 51 Table VIII. Experimental gram and molar s u s c e p t i b i l i t i e s (c.g.s.,e.m.u.) and magnetic moments (B.M.) f o r basic s a l t s of copper (11) aryl-carboxy-l a t e s . Cu(OH)(C 6H 5C0 2) Temp.(°K) 106%S l O 6 ^ 314.7 7.11 1524 304 . 5 7 .32 1567 298 7.54 1611 285.2 7 .75 I 6 5 4 268.2 8 .25 1755 • 248 8.96 I898 229 9.74 2055 209.9 10.7 2249 189.9 12.0 2512 170 . 3 13.4 2795 152 15.6 3239 132.6 17.9 3704 105 . 7 21.9 4512 87 28.4 5825 » e f f > ( B . M . ) 1.93 1.92 1.93 1.92 1.92 1.92 1.92 1.93 1.94 1.94 1.97 1.97 1.95 2.01 Cu(0H)(o- •C1C6H^C02) 362 4.43 1148 1.78 349 4.73 1218 1.81 336 4.92 1263 1.80 322 5.10 1306 1.80 308 5.37 I369 1.80 296 5.58 1419 1.80 283 5.79 1468 1.79 270 6.12 1546 1.80 260 6.31 1591 1.79 246 6.67 I676 1.79 233 7.14 1787 1.80 218 7,50 1872 1.79 203 8.01 1992 1.78 191 8.39 2082 1.77 178 ' 8.90 2202 1.76 164 9.69 2389 1.76 151 10.8 2651 1.78 136 12.0 2934 1.77 121 13.5 3288 1.77 107 15.9 3854 1.81 93 18 .5 4468 1.82 52 ( continue on Table VIII ) Temp.(°K) l O 6 ^ lO^Xm (B.M.) Cu(OH)(m-.C1C6H^C02) 359 4 .94 1268 I .87 3^3 5.16 1320 1.87 327 5.52 1405 I .89 311 5.79 1468 1.88 296 6.16 1556 1.89 288 6.20 1565 1.87 268 6.34 1598 I . 8 3 253 6.74 1693 1.83 238 7.24 1811 I . 8 3 223 7.87 1959 1.85 198 8 .33 2068 1.79 182 9.09 2247 1.79 167 10.4 2556 I . 8 3 150 U . 5 2816 i . 8 3 134 12.9 3146 I . 8 3 118 15.2 3689 1.86 104 17.4 4208 1.86 90 20.8 5011 1.90 Cu(OH)(p-•C1C6H4C02) 370 5.55 1412 2.01 35^ 5.82 1476 2.01 339 6.14 1551 2.02 325 6.46 1627 2.03 310 6.84 1716 2.03 294 7.32 1830 2.05 283 7.46 I863 2.03 267 7.70 1919 2.01 252 8.20 2037 2.00 241 8.69 2153 2.02 226 9.37 2313 2.02 214 9.99 2460 2.03 194 10.8 265I 2.02 181 12.5 3052 2.09 166 13.7 3335 2.09 .152 15.3 3713 2.11 136 17.7 4279 2.15 120 20.9 5034 2.19 105 25.2 6049 2.25 89 31.7 7583 2.32 53 900 700 500 300 A B C D Cu(0H)(C5H5C02) Cu(OH)(0-ClC 6H4C0 2) Cu(0H)(m-ClC 6H4C0 2) Cu(0H)(p-ClC6H4C0 2) Experimental reciprocal' s u s c e p t i b i l i t y , 10-^Xm-l 200 Temp. (°K) F i g . 12. Cryomagnetic data f o r the basic s a l t s of copper (11) aryl-carboxylates. 54 3 - 2. Diffuse-Reflectance Spectra of Anhydrous Copper (11) Aryl-Carboxylates and Related Compounds. The di f f u s e - r e f l e c t a n c e spectra f o r a l l compounds investiga^d i n the present study are shown i n Pigs. 13-16 and Table IX. I t can be seen c l e a r l y that nine out of the eighteen compounds ( including copper (11) benzoate, copper (11) meta-ohlorobenzoate. copper (11) para-chlorobenzoate, copper (11) benzoate monopyridine, copper (11) ortho-chloro-benzoate monopyridine, copper (11) meta-chlorobenzoate mono-pyridine, copper (11) meta-chlorobenzoate monodioxane, copper (11) para-chlorobenzoate monopyridine and copper (11) para-chlorobenzoate hemipyridine. ) show two absorption maxima i n the v i s i b l e region ; one l i e s at 660-688 mp., designated as band 1, and the other at 370-400 nju designated as band 11. Band 1 i s comparatively sharp and intense, whereas band 11 i s weak and broad. The broading of the l a t t e r band sometimes makes i t almost undefinable ; moreover, i t appears as a shoulder on the charge-transfer band. The spectra are i n close conformity with those of the copper (11) n-alkanoates66 i n the c r y s t a l l i n e state and of the copper (11) substituted aryl-carboxylates ^9 i n non-donor solvents. These r e s u l t s are considered to be confirmation evidence that a dimeric structure analogous to that of copper (11) acetate monohydrate i s present i n the above nine complexes i n the c r y s t a l l i n e state. I t must be emphasized here that copper (11) 55 para-chlorobenzoate prepared i n the present study may be a mixture of the dimeric and polymeric forms. This point has been discussed i n the previous section on magnetochemistry. The remaining complexes l i s t e d i n Table IX show only one absorption band at 630-693 ^ i n t h e v i s i b l e region. The spectra have features which are s i m i l a r to those of the copper (11) n-alkanoates i n w a t e r ^ and copper (11) a r y l -carboxylates i n p y r i d i n e 2 ? . I t has been found that both a l k y l - and aryl-carboxylates of copper (11) are not present as dimers i n water or i n pyridine. Therefore, i t i s concluded that those complexes i n Table VIII, which show only one absorption maximum i n the v i s i b l e region are not binuclear but probably possess polymeric structures. This i s i n com-plete agreement with the conclusions reached e a r l i e r on the basis of the magnetic s u s c e p t i b i l i t y r e s u l t s . Normal, mononuclear copper (11) sa l ts6» 2 7 such as copper (11) s u l f a t e i n aqueous s o l u t i o n ^ , show only one d-d t r a n s i -t i o n band at ca. 700-800 mu which Is comparable to the band at 630-693 mu found f o r a l l the complexes In Table IX.. Moreover, the absorption bands of ar y l - c a r b o x y l i c acids** and p y r i d i n e 2 0 appear i n the u l t r a v i o l e t region. Accordingly, the band at 630-693 mu may be ascribed to a ligand f i e l d band of the copper (11) i o n . Following the assignments of Beimann55 et a l . on the spectrum of copper (11) acetate monohydrate, the band at 660-688 mu f o r the dimeric compounds ( Table IX ) may be assigned to the ( d x z , d y z ) — » d x 2 - y 2 t r a n s i t i o n . Such 56 a t r a n s i t i o n w i l l be solvent dependent. For example, coor-dination of a pyridine molecule on the z-axis w i l l lower the s t a b i l i t y of the d x z and d y z o r b i t a l s and so give r i s e to a s h i f t of the absorption band to longer wave lengths. This can be seen c l e a r l y from the s h i f t of the band at 665 mu f o r copper (11) benzoate to 688 mu f o r i t s monopyridine adduct. S i m i l a r l y , the wave lengths of the d-d t r a n s i t i o n bands of the other anhydrous normal s a l t s show a r e d - s h i f t on coor-dination with one pyridine or dioxane molecule per copper atom. Copper (11) benzoate, copper (11) meta-chlorobenzoate and copper (11) para-chlorobenzoate show almost the same two absorption maxima at 660-665 mu and 400 nyu. Obviously, both bands appear i n s e n s i t i v e to the v a r i a t i o n of the carboxylate group. The p o s i t i o n of the band at 660-665 mu can be e a s i l y defined, whereas, i t i s d i f f i c u l t to give an accurate f i g u r e f o r the p o s i t i o n of the band at 400 mju as t h i s band appears only as a shoulder on the charge-transfer band. Copper (11) ortho-chlorobenzoate shows only one absorp-ti o n band at 690 mu. This band has a d i s t i n c t r e d - s h i f t with respect to the corresponding band f o r the other anhydrous aryl-carboxylates of copper (11) ( Table IX ) i n the crysta-l l i n e state. In 1964, Yawney70 observed that the same com-pound shows a d-d t r a n s i t i o n band at 674 mu i n chloroform. His sample and that prepared i n the present study have the same room-temperature moment of 1.62 B.M. i n d i c a t i n g that 57 both samples are of the same form. Yawney also pointed out that t h i s compound shows two absorption bands at 670 + 15 and 382 + 3 mu i n dioxane. The appearance of the band at 382 + 3 wp- was used as evidence f o r the conversion from a polymeric structure to a dimeric one. I t appears that a decrease i n the wave length of the d-d t r a n s i t i o n band.for copper (11) aryl-carboxylates usually accompanies a conver-sion from a polymeric to a dimeric structure. Since the spectrum of copper (11) ortho-chlorobenzoate i n chloroform shows no band i n the 400 DJU region, i t may be assumed that there are no dimeric molecules present and hence the s h i f t i n the wave length of the band at 690 m;u i n the s o l i d to 674 noa i n chloroform can not be explained by a conversion from a polymeric to a dimeric structure. Clearly, more work i s needed on a study of the spectra of t h i s compound and the other copper (11) aryl-carboxylates i n various solvents. A l l the monopyridine adducts of copper (11) aryl-carbo-xylates ( Table IX ) show a band at 684-688 DUI and a weak band at 370-400 mu i n the v i s i b l e region. The presence of a band i n the 370-400 nyu region f o r these compounds may be considered supporting evidence f o r the assignment of a binu-clear structure to them. The absorption maximum of the band at 684-688 mu i s intermediate between 660-665 m*i observed i n the anhydrous s a l t s ( with the exception of the ortho-chloro d e r i v a t i v e ) and 700-800 mu f o r normal mononuclear copper (11) s a l t s ^ . 58 Obviously, coordination of one pyridine molecule per copper atom on the metal-metal axis of the dimeric anhydrous a r y l -carboxylates of copper (11) causes a r e d - s h i f t i n the wave length of band 1. An explanation of t h i s r e d - s h i f t has been given previously ( see page 56 .) • A r e d - s h i f t of band I i s also observed i n going from copper (11) para-chlorobenzoate to i t s hemipyridine adduct. An explanation i n terms of the d e s t a b i l i z a t i o n of the d and d y z o r b i t a l s may be also made i n t h i s case since both the monopyridine and hemipyridine adducts apparently have analogous structures of the M acetate-type M . The mono-p-dioxane adduct of copper (11) meta-chloroben-zoate also shows the two absorption bands c h a r a c t e r i s t i c of binuclear copper (11) complexes. In comparison with the corresponding band f o r the anhydrous meta-chlorobenzoate of copper (11), band I i s only s l i g h t l y higher i n wave length. This difference, although small, may be explained i n terms of a d e s t a b i l i z a t i o n of the d x z and d y z o r b i t a l s on coordina-t i o n with p-dioxane. The above r e s u l t s show that pyridine i s a stronger coor-dinating agent than dioxane towards copper (11). This i s consistent with the findings of Belford-5 et a l . who studied the absorption spectra of solutions of copper (11) ^-diketones i n pyridine and dioxane. The absorption spectra of the dipy r i d i n e adducts of copper 59 (11) aryl-carboxylates show only one d-d t r a n s i t i o n band at 630-683 mu i n the v i s i b l e region. Polymeric copper (11) alkyl -carboxylates66 S U C h as copper (11) formate, have been shown to have one broad d-d t r a n s i t i o n band i n t h i s region. Thus, the broading i n the absorption peak and the disappearance of the band i n the 375 mu region i n the spectra of the dipy-r i d i n e adducts strongly suggests the absence of dimeric struc-tures i n these complexes. The basic s a l t s of copper (11) aryl-carboxylates show only one ligand f i e l d band at 685-693 mu i n the v i s i b l e region. The s i m i l a r i t i e s i n the spectra of the basic s a l t s and the dipyridine adducts of the normal s a l t s suggest s i m i l a r i t i e s i n the structures of these two groups of compounds and support the assignment of polymeric configurations to them. 6o Table IX. Diffuse-reflectance spectra. Complexes Absorption r Maxima (mju) Cu( 0^5002)2 665 (s) 400 (w) Cu(o-C1C6H>C02)2 6 9 0 (vs) Cu(m-C1C6HZ|.C02)2 664 (s) 400 (w,inf.) Cu(p-ClC6Hi|C02)2 660 (s) 400 (w,inf.) Cu(m-CIC5H4CO2)2*P-dioxane 6 7 0 (s) 370 (w) Cu(C6H5CO2)2 * P v r l d i n e 688 (vs) 375 (w) Cu(o-ClC5H4C02)2Pyridine 6 8 5 (vs) 396 (w) Cu(m-ClC5H4C02)2*pyridine 684 (vs) 370 (w) Cu (p- CI C6H4CO2 )2* p y r i dine 686 (s) 370 (w) Cu( p-ClC5HZ),C02 ) 2 i p y r i dine 685 (vs) 400 (w,inf.) Cu(C5H^C0 2) 2* 2pyridlne»H 20 630 (b) Cu(o-ClC5Hij,C02) 2* 2pyridine 650 (b) Cu (m- CI C 5 H Z J . C O 2) 2' 2pyri dine 683 (b) Cu(p-ClC5Hi}.C02) 2* 2pyridine 642 (vb) Cu(0H)(C5H5C02) 685 (vb) Cu(0H)(0-ClC 6H^C0 2) 685 (b) Cu(0H)(m-ClC6H^C0 2) 690 (vb) Cu(0H)(p - C l C 6 H 4 C 0 2 ) 693 (b) s strong ; vs very strong b broad j vb — — very broad w weak ; i n f . — I n f l e c t i o n 61 A i Cu(C6H 5C0 2)2 400 500 600 Wavelength (nyi) F i g . 13. Diffuse-reflectance spectra of anhydrous copper (11) aryl-carboxylates. W a v e l e n g t h (mu) D i f f u s e - r e f l e c t a n c e s p e c t r a f o r m o n o p y r i d i n e , h e m i -p y r i d i n e a n d p - d i o x a n e a d d u c t s o f c o p p e r (11) a r y l -c a r b o x y l a t e s . Wavelength (mu) Pig. 15. D i f f u s e - r e f l e c t a n c e spectra f o r d i p y r i d i n e adducts of copper (11) aryl-carboxylates. -3-vo >> •P •H CO <D rH o -p p. o 3 -P •H o \ \ \ \ A B C D Cu(OH)(C5H5CO2) Cu( OH) (0-0105^002) Cu(OH)(m-ClCgH^COg) Cu(OH) (p.-ClCgH^COg) 400 600 500 Wavelength (nui) F i g . 16. D i f f u s e - r e f l e c t a n c e spectra f o r basic s a l t s of copper (11) aryl-carboxylates. 700 65 3 - 3« Infrared Spectra of Anhydrous Copper (11) Aryl-Car-boxylates and Related Compounds. Infrared data obtained f o r the copper (11) carboxylates and related compounds are given i n Table X-XV. The spectra of copper (11) benzoate and i t s monopyridine and d i p y r i d i n e mono-hydrate adducts are i n reasonable agreement with those reported by Wilkinson, G i l l a r d and H a r r i s ^ , A complete assignment of the frequencies of the t h i r t y - s i x normal vibrations i n the benzoate ion ( In sodium benzoate ) has been given by Lindsey* 6 et a l . and a p a r t i a l assignment of the absorption bands i n the spectra of the compounds studied i n the present work i s achieved by comparing t h e i r spectra with that of sodium benzoate. 3-3-1. 4000-1800 cmT1 region. In a l l compounds studied weak to medium i n t e n s i t y bands occur i n the region 2800-3200 cmT1 and are assigned to C-H stretching v i b r a t i o n s . In the case of the pyridine addition compounds i t Is d i f f i c u l t to determine which C-H stretching bands are due to the pyridine ligands and which are due to the carboxylate ligands ; however, a comparison of the spectra of the anhydrous copper (11) s a l t s and pyridine suggests that the bands due to pyridine occur around 3090-3200 cm!1. McWhinnie^ has examined the i n f r a r e d spectra of some basic s a l t s of copper (11) complexes of the type ((aminopyrl-dlne)Cu(0H)Cl0jJ 2 and assigned the absorption bands at 66 3636-3690 cm7 to the OH stretching v i b r a t i o n . In accordance with t h i s we assign the sharp absorption band which appears at 3650 cm."1 i n the spectrum of the basic s a l t of copper (11) benzoate to the OH stretching v i b r a t i o n . This band i s 50 cm. higher than that reported by Kaeding^ 0 et a l . f o r the same compound. The corresponding OH band i s found at 365O-370O cmT1 f o r the three isomeric chlorobenzoates of copper (11). Copper (11) benzoate dipyridine monohydrate shows two intense bands at 3460 and 3330 cmT1. These absorption bands are reasonably ascribed to OH stretching bands of water. 3-3-2. 1800-1300 cm.'1 region. In the region 1650-1500 cm."1 two strong bands are observed f o r the sodium s a l t s , the anhydrous copper (11) s a l t s and the basic s a l t s . In accordance with the r e s u l t s of Lindsey et a l . , we assign the higher frequency band i n t h i s region to C-C stretching vibrations and the lower frequency band to the antisymmetric COO" stretching v i b r a t i o n . In the case of the pyridine addition compounds, as might be expected, more than two strong bands appear i n t h i s region of the spectrum and f o r each of these compounds we have a r b i t r a r i l y assigned the lowest frequency band to the antisymmetric COO" stretching v i b r a t i o n ( J a ). In a l l of the compounds studied i n t h i s work several strong bands were observed i n the region 1500-1300 cm."1. Again,, consistent with the assignment of Lindsey et a l . , we 67 t e n t a t i v e l y assign the lowest frequency strong band i n t h i s region to the symmetric COO" stretching v i b r a t i o n (-J s ). Values of 0 a and\)s are c o l l e c t e d i n Table XV. As was mentioned i n the introduction, Kuroda37»39 found that the values of^a observed f o r copper (11) dicarboxylates with subnormal room-temperature magnetic moments ( i n d i c a t i o n of a binuclear structure ) are greater than the -Ja values f o r the corresponding sodium s a l t s . However, where the copper (11) carboxylate does not have a binuclear structure Oa f o r the copper (11) s a l t i s eithe r equal to 37»39 or l e s s than ^1 Ja f o r the sodium s a l t . From the data c o l l e c t e d i n Table XV i t may be seen that -»)a f o r copper (11) benzoate, meta-chloroben-zoate and para-chlorobenzoate i s greater, i n each case, than •Oa f o r the corresponding sodium s a l t ; whereas, -Ja f o r copper (11) ortho-chlorobenzoate i s very nearly equal to -^a f o r sodium ortho-chlorobenzoate. Since magnetic and spectral studies described e a r l i e r i n t h i s thesis showed that a l l of these copper (11) carboxylates, except copper (11) ortho-chlorobenzoate, have binuclear structures, our i n f r a r e d data are consistent with the findings of Kuroda described above. I t i s c l e a r that the difference between Oa f o r the copper (11) s a l t of a carboxylic a c i d and -va f o r the sodium s a l t of the same a c i d depends on the configuration of the carboxylate bridging i n the copper (11) s a l t . I t may be concluded, therefore, that since Ja f o r each of the basic s a l t s 68 l i s t e d i n Table XV i s the same as -Ja.for the corresponding sodium s a l t , the basic s a l t s have s i m i l a r structures with s i m i l a r carboxylate bridging configurations. Moreover, the f a c t thatOa f o r each of the monopyridine derivatives l i s t e d i n Table XV i s greater than -)a f o r the corresponding sodium s a l t i s at l e a s t consistent with a s i m i l a r structure f o r these compounds and f o r the same reason I t may be argued that the i n f r a r e d r e s u l t s are consistent with a l l the dipyridine derivatives having s i m i l a r structures. Lecomte2*-0 et a l . have suggested that the difference be-tween the two COO" stretching frequencies (A-0= - 0 s ) In . carboxylates i s dependent, i n part at l e a s t , on the equivalence of the two C-0 bonds i n the carboxylate group. Thus, A-) values f o r carboxylic acids are i n general l a r g e r than ^0 values f o r the corresponding sodium salts29>4o,51 due to the f a c t that the two C-0 bonds are equivalent i n the case of the sodium s a l t s but not equivalent i n the case of the free acids. We f i n d , i n the present work, that the l v a l u e s f o r sodium ben-zoate and the three isomeric chlorobenzoates are smaller than the A0 values f o r the respective free acids. Values of - ^ J f o r the copper (11) aryl-carboxylates and t h e i r pyridine addi-t i o n compounds are l i s t e d i n Table XV and i t i s i n t e r e s t i n g to note that i n a l l cases AO increases i n the order basic salt< < a - J normal salt< monopyridine adduct < •aO dipyridine adduct. This suggests that the difference between the two C-0 bonds 69 i s greatest f o r the di p y r i d i n e adduct a r e s u l t which i s con-sis t e n t with the structure, proposed e a r l i e r f o r these comp-ounds, involving unsymmetrical carboxylate bridging. 3-3-3. 1300-800 cm."1 region. Several bands, due mainly to C-H v i b r a t i o n s ^ occur i n t h i s region of the spectrum of a l l the compounds studied. Also, i n the case of the chlorobenzoate derivatives, bands due to C-Cl stretching vibrations-^ 0 presumably occur In t h i s region although no attempt was made to i d e n t i f y these. A strong doublet band ( 940-920 cm."1 ) observed i n the spectrum of the basic s a l t of copper (11) benzoate i s absent from the spectrum of sodium benzoate and copper (11) benzoate and may therefore be due to the M-O-H bending mode. Sim i l a r bands are observed i n the spectrum of the basic s a l t s of copper (11) ortho-, meta- and para-chlorobenzoate ( 955» 9^0-915 ahd 925-880 cm."1, respectively ). 3_3-4. 800-400 cm. - 1 region. In t h i s region the absorption bands due to benzene ring deformation v i b r a t i o n , COO" symmetric deformation, COO" rocking vibrations and out-of-plane r i n g deformation vibrations and i n the case of the chlorobenzoates C-Cl deformation v i b r a -tions occur. In the case of the copper (11) complexes a very strong band which i s absent from the spectra of the sodium •1 s a l t s appears i n the region 725-773 cm. . The frequency of t h i s band i s too high f o r i t to be simply due to the Cu-0 70 stretching v i b r a t i o n i n view of the f a c t that Satake* et a l . reported the Cu-0 stretching v i b r a t i o n to occur at 66^670 cm." i n the copper (11) n-alkanoates. Pyridine shows fundamental absorption bands at 7^9, 703, 604 and k0$ cm."1. The band at 703 cm."1 i s masked by absorp-t i o n due to the carboxylate ligands In the copper (11) carboxy-la t e - p y r i d i n e addition compounds. The other three pyridine bands are r e a d i l y observed, however, and are found at s l i g h t l y higher frequencies than i n the pyridine. This s h i f t i n g can be a t t r i b u t e d to the coordination of pyridine to the metal ion and i s i n agreement with the r e s u l t s of Clark and Williams . who investigated the e f f e c t on the frequencies of the pyridine vibrations i n d i p y r i d i n e complexes of divalent m e t a l l i c s a l t s . 71 Table X. I.E. absorption frequencies i n some sodium carboxylates. CgHrCC^Na o-ClCDHZ|.C02Na m-ClCDH^C02Na p-ClCgH^COgNa Assign-. "* . ment 3100 (w) 3090 (w) 2950 (w) 1954 (w) 1903 (w) 1621 (w) 1595 (vsf) 1554 (s) 1520 (sh) 3100 (w) 3030 (w) 3000 (w) 2800 (w) 1925 (w) 1610 (w) 1580 (vs) 1560 (s) 1532 (sh) 3100 (w) 2950 (w) 2770 (w) I633 (w) 1599 (vs) 1565 (sh) 1555 (s) 15^5 (sh) 1520 (sh) 2950 (w){ 2800 (w)) 1970 (w) 1670 (vw) 1620 (w) 1600 (vs) 1548 (s) 1488 (vw) 1422 (s) 1413 (s) 1400 (s) 1390 (s) 1410 (s) ' 1390 (sh) (m) 1365 (w) 1305 1301 (sh) 1290 (m) 1270 (w) 1275 (w) 1265 (m) 1280 (w) 1236 (w) 1255 (w) 1250 (w) (w) 1170 (w) 1178 1162 (m) 1120 (w) 1140 (m) 1137 (w) IO65 1105 (s) (m) 1053 (m) 1075 (m) 1085 (m) 1030 (m) 1032 (w) 1005 (w) 1022 (m) 1006 (w) 974 (w) 980 (w) 960 (wb) 925 (w) 920 (vw) 900 (w) 879 (m) 870 (w) 862 (m) 853 (m) 855 (m) 852 (m) C-H s t r . Benzene r i n g v i b . Antlsym. C02~str. C02~sym. def. C-C s t r . Sym. CO2 s t r . ( continue on next page ) 72 ( continue on Table X ) C6H5C02Na .Oz-ClCgH^COgNa m-ClCgHj^COgNa p-ClCgHljsCC^Na Assign-• • ~~ ment 825 (m) 818 (w) 709 (s) 683 (s) 680 (s) 526 (b) 418 (wb) 752 (s) 742 (s) 719 (s) 709 (s) 685 (s) 646 (s) 537 (b) 497 (b) 467 (b) 453 (b) 829 (w) 821 (w) 758 (s) ?40 (s) 670 (s) 658 (m) 535 .(b). 493 (b) 770 (s) 683 (s) Benz. r i n g v i b . C02~sym. def.and C-Cl def. modes 532 (s) C0 2" rocking 525 (sh) 469 (m) Out-of-plane r i n g deform. 415 (b) 73 Table XI. I.R. absorption frequencies i n anhy-drous copper (11) aryl-carboxylates. Cu(C5H 5-co 2 ) 2 Cu(o- •C1C6HV Cu(m- ClCgRV C0 2)2 Cu(p-C1C6HV Assign-— C 0 2 ) 2 ment 3090 (w)i 3110 (w)| 3110 (w)l 3120 (w)] 3065 (w) 1 3110 (w)( C-H s t r . 3030 (w), 2960 (w)J 2980 (w)3 2250 (w) 2900 M) 2880 1954 (w) 1954 (w) 1930 (w) 1903 (w) 1880 (w) 1805 (w) 1820 (w) 1773 (w) 1730 (w) 1680 (w) 1621 (w) 1610 (s) 1610 (s) 1618 (s) 1600 (s) Benzene 1600 (sh) 1600 (w) r i n g v i b . 1580 (w) 1575 (w) 1565 (s) 1562 (s) 1570 (s) 1560 (s) Antisym. 1535 (sh) 1532 (m) 1537 (m) , C02- s t r . 1520 (sh) 1520 (sh) 1500 (m) 1475 (m) (s) (w) 1442 (w) 1430 (s) 1428 1495 1410 (sh) 1412 (s) 1410 (s) 1395 (s) 1403 (s) Sym. C02~ 1405 (sh)j 1400 (sh) s t r . 1315 (vw ) 1305 (w) 1300 (w) (w) 1298 (sh) 1288 (w) 1280 1270 (vw) (w) 1270 (m) 1270 (vw) 1255 1255 (w) 1248 (w) 1180 (vw) 1170 (w) 1170 (w) 1160 (w) II63 (w) (w) (w) 1155 (m) 1145 (w) 1150 1120 1113 (m) 1102 (vw) ( continue on next page ) 74 ( c o n t i n u e o n T a b l e X I ) Cu(C6R~5- Cu(o-ClC6HV CuCm-ClCgHzj- Cu(p-C1C6B>- A s s i g n -C 0 2 ) 2 C 0 2 ) 2 C 0 2 ) 2 - C 0 2 ) 2 m e n t 1072 (vw) 1097 (w) 1090 (m) 1064 (w) - 1055 (m) 1088 (w) 1030 (m) 1038 (m) 1078 (m) 1071 (m) 1062 (w) 1040 (w) 1020 (m) 1012 (w) 1005 (w) 1003 (w) 980 (w) 952 (w) 975 (w) 937 (m) 935 (w) 923 (w) 953 (w) 915 (w) 855 (w)7 870 (w)7 897 Ml 863 (m) 845 (w)J 855 (w)I 893 (w)J 857 (m) 820 (w) 886 (w) 852 (m) 788 (w) 882 (w) 845 (w) 872 (m) 840 (w) 732 ( s ) 757 ( s h ) 770 ( s ) 773 ( s h ) C u-0 s t r . 718 ( s ) 748 ( s ) 757 ( s ) 768 ( s ) B e n z e n e 747 ( s ) r i n g v i b . 695 ( s ) 731 ( s ) 737 ( s ) C O o - s y m . 688 ( s ) 725 ( s ) d e f . a n d 702 (w) 695 (w)? C-Cl d e f . 683 (m) 683 (w)) m o d e s 660 ( s ) 675 (m) 655 ( s ) 662 (m) 612 (m) 513 (m) 512 ( b ) 502 ( b ) 577 (m)? C 0 ? - r o c k -556 (m)i. i n g 480 (m) 487 ( b ) 480 ( b ) 477 (m) O u t - o f -468 ( b ) p l a n e r i n g d e f . 75 Table XII. I.E. absorption frequencies i n basic s a l t s of copper (11) aryl-carboxylates. C u ( O H ) - C u ( O H ) - C u ( O H ) - C u ( O H ) - Assign-. (C5H^C02) (0-CIC5H4CO2) (m-ClC5H^C02) (p-ClC6HZ|,C02) ment 3650 (m) 3650 (m) 3650 (a) 3700 (a) •OH s t r . ' 3100 (w) 3110 (w) 3130 (w) 3000 (w) (w) 2960 (w) 2950 2950 (w) 2950 U) 2800 (w) 2760 (w) 2550 (w) 1965 (w) I603 (s) 1950 (w) 1610 (sh) 1605 (sh) 1570 (sh) 1595 (s) 1588 (s) 1587 (s) Benzene rin g vib 1553 (s) 1560 (s) 1550 (s) 1548 (s) Anti sym. 1465 (w) C0 2~str. 1^30 (s)i 1430 (s) ) 1430 (s) 1424 ( s ) j C-C s t r . 1415 (s)S 1412 (s) 1410 (sh) 1418 (s)J Symm. CO 1402 (sh)i 1395 (s) , s t r . 1375 (m) 1345 (w) 1350 (w) 1340 (w) 1335 (w) 1310 (w) 1270 (vw) 1265 (w) 1288 (w) 1280 (m) 1255 (w) 1265 (w) 1270 (w) 1185 (w) 1235 (w) (w) 1175 (w) 1155 -(w) 1150 1170 (w) 1145 (w) 1060 (m) 1145 (w) 1097 -(w) 1070 (w) 1105 (w) 1072 (m) 1100 (m) 1055 (vw) 1045 (m) 1087 (w) ( continue on next page ) 76 ( continue on Table XII ) Cu(OH)- Cu(OH)- Cu(OH)- Cu(OH)- Assign-(C5H5CO2) (O-C1C6H^C0 2) (m-ClC 6H4C0 2) (p-ClC 6H4C0 2) ment 1030 (m) 1023 (m) 1018 (vw) 1005 (vw) 957 (vw) 9^0 (s) 7 955 (s) 940 (m)7 925 (s) 920 (vs)} - — 915 (s)J 883 (sh) 877 (m) 895 (w) 876 (s) 850 (m) 860 (w) 880 (w) 855 (m) 817 (w) 780 (w) 748 (w) ?20 (sh) 753 (sh) 770 (w) 770 (s) 703 (s) 745 (s) 755 (s)] 765 (s) • 742 ( 8 ) 1 730 (w) 685 (m)l 725 (s)| 665 (m) '683 (m)7 680 (m)5 688 (m) 630 (w)l 652 (s)j 562 (b) 5^3 (b) 545 (b) 570 (m)7 (b) 545 (a)! 507 485 (b) 465 (b) 495 (b) 470 ^77 (b) 463 (wb) 450 (b) OH bend-ing Cu-0 s t r . Benzene r i n g v i b . COp-sym. def.and C-Cl def. modes CO2"rock-ing Out-of-plane r i n g deform. 77 Table XIII. I.E. absorption frequencies i n mono-pyridine adducts of copper (11) a r y l -carboxylates, CufX-CgH^CC^)2*( c 5 H 5 N)n n = 1 X = H n = 1 X = o-Cl n = 1 X = m-Cl n = 1 n = f Assign-X = p-Cl X = p-Cl ment 3090 (m) 3090 (w) 3000 (w) 2950 (w) 2830 (w) 2000 (w) 1930 (w) 1840 (w) 1640 (w) I636 (s) 1615 (sh) 1605 (sh) 1576 (s) 15^5 (sh) 1495 (m) 1480 (m) 1445 (s) 2930 (w) 2650 (w) 2260 (w) 1980 (w) 1700 (w) 1645 (sh) I632 (s) 1602 (s) 1575 (s) 1482 (s) 1470 (s) 1435 (s) 1319 (m) 1282 (w) 1238 (w) 1383 (sh) 1360 (w) 1318 (w) 1255 (w) 3140 (w) 2950 (w) 2330 (w) 1800 (w) 1640 (s) 1610 (s) 1575 (s) 1480 (m) 1470 (w) 1448 (m) 1418 (s) ? 1425 (s) 1422 (s)i 1410 (s) 1398 (s)> 1405 (sh)) 1393 (s) 1290 (w) 1265 (m) 3100 (w) 3100 (w) 2950 (w) 2880 (w) 1920 (w) 1640 (s) 1600 (s) 1570 (s) 1445 (s) 1410 (s)' 1400 (s)J 2950 (w) 2880 (w) 2540 (w) 2260 (w) 1620 (s) 1595 (s)-1568 (s) 1550 (sh) 1530 (m) 1480 (w) 1485 (s) 1445 (s) 1410 (sh)i 1400 (s)I 1372 (sh) Pyridine ri n g v i b . Antisymm. C 0 2 " s t r . C-C s t r . Symm. CO2" s t r . 1277 (w) 1277 (s) ( continue on next,page ) 78 ( continue on Table XIII ) n = 1 X = H n = 1 n = 1 n = 1 n = | X = o ,-Cl X = m-Cl X = p -CI X = p -CI 1220 (w) 1210 (m) 1222 (w) 1220 (s) 1168 (w) 1170 (w) 1172 (s) 1150 (w) 1085 (w) 1150 (w) 1145 (s) 1122 (vw) 1088 (m) 1090 (s) 1075 (w) 1065 (m) 1070 (w) 1076 (m) 1055 (s) 1038 (m) 1040 (m) 1040 <m) 1030 (s) (s) (s) 1012 (m) 1012 (m) 1018 1018 Assign-ment 1216 (s) 1173 (w) 1150 (m) 1055 (vw) 1038 (s) 1031 (s) 1013 (s) 1003 (m) 895 (vw) 887 (w) 821 (m) 818 (m) 750 (w) 915 W> 881 (w) 854 (m) 838 (w) 822 (w) 808 (w) 785 (w) 757 (s) 908 (w) 902 (w) 880 (w) 864 (sh) 856 (s) 850 (w) 858 (m) 851 (m) Pyridine r i n g vib. 718 (s) 750 (s) 770 (s) 773 (sh) 772 (s) Cu-0 s t r . 730 (w)| . 755 (s)) 768 (s)' 765 (s) 0-C-C v i b . 700 (s) 715 (w)i 740 (s ) i 695 (s) 723 (w) 748 (w) 675 (w) 700 (s) 720 (w) 730 (w) Pyridine r i n g v i b . 695 (m)j 652 (s) 678 (m)7 692 (m) 692 (w) C 0 2 ~ sym. 693 (m)i 673 (m)} def. 660 (m) 685 (w) 628 (w) 628 (s) 630 (m) 627 (w) 629. (w) Pyridine r i n g vib. 498 (sh) (m) ^-560 (b) 487 (b,m) 500 (b,m) 485 (b,m) 558 C 0 2 ~ rock-ing 477 (w) 419 (w) 417 (w) 417 (w) 417 (w) Pyridine r i n g vib. 79 Table XIV. I. R. absorption frequencies i n d i p y r i -dine adducts of copper ( 1 1 ) a r y l - carbo-xylates. Cu(C5H 5C0 2) 2 Cuto-ClCgH^- Cudn-ClCgH^- Cu(p-C1C DHV Assign-•2pyH 20 . C0 2) 2'2py C0 2T 2.2py C0 27»2py ment 3^60 3330 3140 3025 2980 2240 1930 1835 1670 I630 (s) (s) (w) (w) (w) (w) (w) (w) (w) (n) 1613 (s) 1565 (s) 1480 (m) 1449 (s) 1390 1370 1298 1236 1218 1206 1176 1168 1165 (s) (s) (w) (w) (s) (w) (w) (w) (w) 3200 (m) 3100 (m) 2800 (w) 2440 (w) 1615 (s) 1600 (s) 1563 (s) 1495 (m) 1473 (s) 1448' (s) 1435 (m) 3110 (m) 1410 (sh) 1410 (vw) 1375 ( s ) l 1353 (s ) J 1340 (sh) 1235 (w) 1215 (m$ 1200 (vw) 1153 (m) 1135 (vw) 2950 2760 1640 I632 1612 1570 1505 1488 1470 1450 1422 1400 1397 1368 1290 1263 1238 1218 w) w) sh) s) s) s) vw) m) vw) s) s) w) s) s) vw) vw) vw) w) 3100 (w) 3000 (w) 2900 (w) 2800 (w) 2650 (w) 1655 (w) 1620 (s) 1570 (s) 1555 (s) 1485 (m) 1450 (m) 1400 (s) 1380 (s) 1290 (vw) 1155 (w) 1275 •1250 1235 1213 1200 1172 1162 1158 (m) (vw) (vw) (s) (vw) (s) (m) (m) C-C s t r . Antisymm. C02~ s t r . C-C s t r . Symm. C O 2 " s t r . ( continue on next page ) 80 ( continue on Table XIV ) C u ( C D H 5 C 0 2 ) 2 C u ( o - C l C 5 H V C u d n - C l C g l f y - C u f p - C l C g H j p •2py.H20 C0 2 T 2 »2py C0 2 7 2 °2py C0 2 7 2 .2py Assign-ment 1140 1072 1045 1035 1032 1021 1012 987 975 950 938 920 849 840 829 822 690 675 (w) (s) (s) (m)l (m)j (m) (w) (vw) (vw) (vw) (w) (vw) (vw) (m) (w) (w) 760 (m) 753 (m) 730 (s) 718 (s) (s) (s) 1120 (w) 1068 (s) 1050 (s) 1033 (s) 1023 (vw) 1018 (vw) 990 (vw) 958 (w) 900 (b) 858 (vw) 838 (sh) 832 (sh) 823 (s) 803 (vw) 763 (sh) I O 8 5 (vw) 1075 (w) 1045 (m) 1015 (vw) 910 (w) 873 (m) 828 (vw) 1140 1108 1098 1090 1070 1045 1038 1019 1007 (m) (vw) (s) (s) (s) (s) (vw) (s) (vw) 953 (vw) 890 (vw) 876 (w) 874 (w) 865 (m) 856 (s) 848 (w) 837 (w) 752 (s) 770 (s) 772 (s) 720 (s) 755 742 (s)[ (s)t 758 (s) 700 668 (s) (w) 695 (s) 650 (s) 673 660 (W )7 690 (s) 639 (m) 643 625 (w) (w) Pyridine r i n g v i b. Cu-0 s t r . 0-C-C C0 2~ def, ( c o n t i n u e on next page ) 81 ( continue on Table XIV ) Cu(C5H5C02)2 CuCo-ClCgH^- Cudn-ClCglfy- Cufp-CICgH^- Assign-•2py.H 2 0 C 0 2 T 2 , , 2 p y C 0 2 ) 2 ' 2 p y C 0 27 2 * 2 p y ment 640 (m) 618 (m) 642 (s)j Pyridine 628 (m)J r i n g v i b . 512 (w) 585 (b) 553 (b) 518 (b) 485 (b) 493 (b) 487 (b) 481 (w) 462 (m) 465 (b) 437 (m) 438 (b) 437 (b) 438 (b) 415 (b) 82 Table XV. Most important frequencies found i n i n f r a r e d absorption spectra of copper (11) a r y l -carboxylates and rela t e d compounds, ( cm."1 ). Compound coo- s t r . C-0 OH s t r . OH bendir Antisym. C00" , Symm. C00" NaOCOC5H5 1554 1413 141 Cu(C6H5C0 2) 2 1565 1412 153 Cu(0H)(C6H"5C02) 1553 1415 138 3650 9401 920> Cu(C5H 5C0 2) 2»py 1576 1398 178 Cu(C5H5C0 2) 2«2pyH 20 1565 1370 195 3460 (H 20) NaOCOC0H>Cl-(o) 1560 1400 160 Cu(o-ClC5Hi|C02)2 1562 1410 152 Cu(0H)(S-ClCgHi|C02) 1560 1412 .148 3650 955 Cu(o-ClC5Hi),C02)2,Py 1575 1405 170 Cu(o-ClC5H^C0 2) 2»2py 1563 1375 188 NaOCOC^Gl-tm) 1555 1390 165 Cu(m-ClC5Hi|,C02)2 1570 1395 175 Cu(OH)(m-ClC6H2],C02) 1550 1395 155 3650 940) 915J Cu(m-ClC5H2j,C02) 2»py 1575 1393 182 Cu(m-C1C6H^C02)2'2py 1570 1368 202 NaOCOCgH^Cl-fp) 1548 1410 138 Cu(p-C1C5H2|C02)2 1560 1403 157 Cu(0H)(p-ClCgH4C0 2) 2 Cu(p-ClC 6H^C0 2) 2•ipy 1548 1568 1418 1400 130 168 3700 925} 880 j Cu(p-ClC6HIj.C02) 2»py 1570 1410 160 Cu(p-ClC6Hi|C0 2) 2. 2 p y 1555 1380 175 83 BIBLIOGRAPHY (1) Asai, 0 . , K i s h i t a , M., and Kubo, M., Naturwissenschaf-ten 9 46, 1 2 (1959). Asai, 0 . , K i s h i t a , M., and Kubo, M., J . Phys. Chem., £3, 96 (1959). (2) Barclay, G. A., and Kennard, C. 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