Complexes of 1, 8-naphthyridines with elements of the first transition series by Ahmad Emad A thesis submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in . CHEMISTRY Montana State University © Copyright by Ahmad Emad (1971) Abstract: Twenty-three new complexes of 1,8-naphthyridine (NN) and 2,7-dimethyl-1,8-naphthyridine (dmNN) with transition metals have been prepared and characterized. These complexes have been classified according to the anion for purposes of discussion. Five halide complexes, four with copper(II) and one cobalt(II) complex with NN or dmNN were synthesized. Among these, two magnetically anomalous complexes, Cu(NN)Cl2 and Cu(NN)Br2 , were discovered. The possible structural geometries have been discussed. Transition metal complexes of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II), and sliver(I) perchlorates with NN were isolated. Chelation of NN with the divalent metal ions and monodentate coordination with silver(I) ion has been suggested. Eight nitrate complexes of NN with the same transition elements have been prepared. Coordination of the naphthyridine molecule was found to be similar to that of the perchlorate compounds. In several of these complexes, coordination of the nitrate ions or water molecules is indicated by the infrared spectra. The chemistry of complexes of this ligand with copper(I) ion was also studied. Four copper(I) complexes containing chloride and perchlorate anions with NN and dmNN were prepared. The possible coordination of the ligands and complexes is discussed and tentative structures proposed.  COMPLEXES OF I, 8 -NAPHTHYRIDINES WITH ELEMENTS OF THE FIRST TRANSITION SERIES by AHMAD EMAD A th e s i s subm itted to th e G raduate F acu lty in p a r tia l fu lf illm en t o f th e requ irem en ts for the d eg ree o f DOCTOR OF PHILOSOPHY in . CHEMISTRY Approved: h tr , M ajo r D epartm en t Chairm an, Exam ining Comm ittee G raduatefD ean MONTANA STATE UNIVERSITY Bozem an, M ontana A ugust, 1971 i l l ACKNOWLEDGEMENT The au th o r w ish e s to e x p re ss h is s in c e re g ra titu d e to D r. K enneth . Emerson who d ire c te d th is re s e a rc h and to thank him for h is a d v ic e , g u id ance and in v a lu ab le i d e a s , bo th in experim en ta l work and in the com position o f th is th e s i s . S p ec ia l th ank s a re ex tend ed to th o se members of. th e fa cu lty and fr iend s who d ire c tly o r in d ire c tly en cou rag ed and a id ed ; and to Dr. G . A. C ro sby and D r. Howard Sandberg for pe rm itting th e au th o r to use. th e C ary 14 and D iffu se R eflec tan ce A ttachm ent a t W ash ing ton S ta te U n iv e rs ity , P u llm an , W ash in g to n . TABLE OF CONTENTS V i t a ............................................. 11 A ck n ow le d g em en t................................ i l l Table o f C o n t e n t s ............. ............................................................. ...................... Iv L is t o f T ab les .................... ...................... .......................................................... ... v i L is t o f F i g u r e s ............................................................................................................. v ii i A b stra c t ...................................................................... ix INTRODUCTION ........................................................... I R eview of L ite ra tu re . ............................................................................... I I , 8 -N aph th y rid in e s and Their C om plexes ............ .............. 3 N itrogen C om plexes of C o p p e r ( I ) ............................... 9 Aims o f This R e s e a r c h ................... 11 EXPERIMENTAL................... 13 A na ly tic a l T echn iques .......................................... 13 P rep a ra tio n o f Compounds .................................... 18 I . H a lide C om p le x e s .............. 18 II . P e rch lo ra te C om p le x e s ............................................. 21 III . N itra te C om plexes .................................................................. 24 IV. Copper(I) C om plexes 28 PAGE RESULTS AND DISCUSSION ........................................................................... 31 Part I — H a lid e C om plexes . . ........................................... 31 Part II — P e rch lo ra te C om plexes ................................................. 57 Part III — N itra te C o m p le x e s .......................................................... 72 P art IV — Copper(I) C om p le x e s ................................................. ... . 87 APPENDIX ................................................................................................................ 98 V PAGE LITERATURE CITED 105 v i I . II. H I. IV. V. VI. VII. ■ V ii i . IX. X. XI. XII. XIII. XIV. XV. XVI. XVII. XVIII. XIX. XX. XXI. TABLE LIST OF TABLES The pKC V alues o f D iffe ren t A romatic A m in e s .............................. 3 H a lid e C om pound s ...................................................................................... 20 P e rch lo ra te C om pound s .................................................... 23 N itra te Compounds . . , . ..................................................................... 27 Copper(I) C om p o u n d s ............................. 30 M agne tic S u s c e p tib i l i ty o f D a ta o f H a lide C om plexes . . . . 32 S e le c ted In fra red A bsorp tions o f H alidp Com plexes . . . . . . 37 PAGE In fra red A bso rp tion s o f Some Cu(II) C om plexes ....................... 40 V is ib le A bsorp tion S pec tra o f H a lid e C om p le x e s ....................... 43 E lec tro n ic A bsorp tion S pec tra o f Some Cu(II) H a lid e s . . . . 46 S e le c ted In fra red A bso rp tions o f C uWmNN^X g.......................... 48 U ltra v io le t A bsorp tion S pec tra o f H a lide C o m p le x e s ............. 53 S e le c ted In fra red A bso rp tions o f P e rch lo ra te C om plexes . . . 58 D iffu se R e f le c tan ce S pec tra o f P e rch lo ra te C om plexes . . . . 62 E lec tro n ic A bsorp tion S pec tra o f P e rch lo ra te C prpp lexes . . . 63 C ry s ta llo g ra p h ic D a ta o f P e rch lo ra te C om plexes .................... 65 U ltra v io le t A bsorp tion S pec tra o f P e rch lo ra te C om plexes . . 69 S e le c ted In fra red A bsorp tions o f N itra te C om plexes ............. 73 R eflec tan ce S pec tra o f N itra te C om plexes . . . . . . . . . . . 76 In fra red Bands o f N itra te I o n .............................................................. 77 In fra red A bsorp tion Bands o f Some N itra te C om plexes . . . . 78 TABLE PAGE XXII. U ltra v io le t A bso rp tion S pec tra o f N itra te C o m p l e t e s .............. 84 XXIII. S e le c ted In fra red A bsorp tions o f Copper(I) C om plexes . . . . 89 XXIV. U ltra v io le t A bsorp tion S pec tra o f Copper(I) C om plexes . . . 95 XXV. S u lfa te C om plexes .....................................................................................103 XXVI. A ceta te C om plexes v ii 104 LIST OF FIGURES FIGURE ' PAGE 1 . H e te ro cy c lic M o lecu le s C on ta in ing Two N itrogen Atoms . . . . 4 2 . Bis( 1 ,8 -naph thy rid ine) copper(II) ch lo rid e ........................................... 6 3 . S tru c tu re o f T e trak is ( 1,8 -n aph th y rid in e (iro n (II )p e rch lo ra te . . . 8 4 . S chem atic D iagram o f th e Io n -ex ch an g e c o l u m n ............. ... . . . 14 5 . M agn e tic S u s c e p t ib i l i t ie s o f th e Subnormal Copper(II) C om plexes . ....................... ....................................................................... 34 6. P o s s ib le S tru c tu res for Cu(NN)Clg and C u (N N )B rg ....................... 35 7 . In fra red S pec tra o f OMCP jgNg and C gH gN g .......................... ... . . . 38 8 . In fra red S pec tra o f Cu(CgHgNg)Clg and C ^C gH gN g ^C lg • • • 39 9 . D iffu se R e flec tan ce o f H a lid e C om plexes ........................................ 42 10. In fra red S pec tra o f C u(C gH gNg)^" 4 HgO and C u(C 8H6N2)4(C lO 4)2 .................................................................................. 61 11. In fra red S pec tra o f Cu(CgHgN2) 2 ^g(NOg)2 and C u(C 8H6Ng)2(NO3)2 .................................................................................. 79 12. In fra red S pec tra o f OLEOMCPMCXSFSOI,8 Cu(CgHgN2)ClO4 .................................... '................................................... 90 13. S ugg es ted S truc tu re for Cu(NN)ClO4 C om p le x ................................ 91 14. S tru c tu reb f(CH gN =NCH g)C ugC lg C om p o u n d .............................. . 96 v ii i ix ABSTRACT Tw en ty -th ree new com p lexes o f 1 ,8 -naph thy rid in e (NN) and 2 ,7 -d im e th y l- l /8 -n ap h th y rid in e (drpNN) w ith tra n s it io n m e ta ls have been p rep a red and c h a ra c te r iz e d . These com p lexes h^ve been c la s s i f ie d acco rd in g to th e an ion for p u rp o se s o f d is c u s s io n . F ive h a lid e c om p le x e s , four w ith copped II) and one cobalt(II) com plex w ith NN or dmNN w ere s y n th e s iz e d . Among th e s e , two mag­ n e t ic a l ly anom alous com p lex e s , Cu(NN)CI2 and Cu(NN)Brg , w ere d i s ­ co v e red . The p o s s ib le s tru c tu ra l g eom etrie s have been d is c u s s e d . T ran s itio n m e ta l com n lexes o f m anganese(II), Cobalt(II), n icke l(II) , copper(II), z inc(II), and s l iv e d I) p e rc h lo ra te s w ith NN were is o la te d . C h e la tio n o f NN w ith th e d iv a le n t m e ta l io n s and m onoden ta te c oo rd in a ­ tion w ith s ilv e r(I) ion h a s b een su g g e s te d . E ight n itra te com p lexes o f NN w ith th e sam e tra n s i t io n e lem en ts h ave been p re p a red . C oo rd in a tion o f th e n aph thy rid in e m o lecu le was found to be s im ila r to th a t o f th e p e rc h lo ra te com pounds. In s e v e ra l o f th e s e com p lex e s , coo rd in a tio n o f th e n itr a te io n s or w a te r m o lecu les is in d ic a te d by th e in fra red s p e c t r a . The ch em is try o f com p lexes o f th is lig an d w ith copper(I) ion w as a ls o s tu d ie d . Four copper(I) com p lexes co n ta in in g ch lo rid e and p e r­ c h lo ra te an ion s w ith NN and dmNN w ere p rep a red . The p o s s ib le coo rd in a tio n o f th e lig an d s and com p lexes is d is c u s s e d and te n ta tiv e s tru c tu re s p ro po sed . IN T R O D U C T IO N REVIEW OF LITERATURE: In re c e n t y e a r s , th e re h a s been some in te r e s t in t ra n s it io n m etal com p lexes o f h e te ro c y c lic m o le c u le s , co n ta in in g two n itrog en a tom s , form ing four-m em bered ring c h e la te s (1 ,2 ,3 ) . M ost o f th e common c h e la tin g ag en ts form f iv e - or s ix -m em bered ring s and l i t t l e is known abou t th e c h e la tin g pow ers o f a g en ts form ing four-m em bered r in g s . The n itrog en h e te ro c y c le s a b le to form five -m em bered ring c h e la te s have long b een s tu d ie d (4 ,5 ,6 ) . The exam p les o f th e s e are: 2 ,2 '-b ip y r id in e , 1 ,1 0 -p h en an th ro lin e , and th e ir d e r iv a t iv e s . These m o lecu le s a re good rr-bonding lig an d s and th e ir s trong c ry s ta l f ie ld p ro p e rtie s a re p a r tia lly due to th e ir a b il i ty to p a r t ic ip a te in n -bond ing w ith th e m eta l a tom s (7 ). The compound 1 ,8 -naph thy rid in e and i ts d e r iv a tiv e s by com parison form four-m em bered ring c h e la te s ra th e r th an f iv e . Ion ic l ig a n d s w hich form four-m em bered c h e la te rin g s have been known for a long t im e , and th e ir com p lexes a re s ta b i l iz e d by io n ic c h a rg e s . Examples o f th e s e are: p e rc h lo ra te s (8 ,9 ) , n i t r a te s (10), c a rb o n a te s (11), and c a rb o x y la te s (12). The s im ila r ity o f c h e la te d 1 ,8 -naph thy rid in e com plexes to c h e la te com ­ p le x e s o f a c e ta te ion s s u g g e s ts th a t n aph th y rid in e s m igh t form po ly ­ n u c le a r com p lexes w ith copper o r o th e r tra n s it io n m e ta l s , a s a c e ta te do es in a few c a s e s . Among th e s e a n io n ic l ig a n d s , th e ca rb oxy la te io n s have been m ost tho rough ly s tu d ie d . They may co o rd in a te th rough one o r both 2oxygens and th ey a ls o form a c la s s o f p o ly n u c le a r m o lecu le s w ith m e ta l-m e ta l in te ra c t io n s w here the c a rb oxy la te group c o o rd in a te s a s a b id e n ta te lig and to two m e ta l a tom s . A la rg e number o f th e s e com plexes have b een in v e s t ig a te d and c h a ra c te r iz e d w ith copper(II) io n s (12). D im eric copper(II) c a rb o x y la te s show unu sua l m agne tic p rope r­ t i e s . They e x h ib it a m agne tic moment l e s s th an 1.7 B. M . compared w ith th e v a lu e o f 1.8-2.2 B .M . for norm al copper(II) com pounds. The m ag­ n e tic s u s c e p t ib i l i ty o f th e s e com p lexes does not obey th e C u rie -W e is s law . I t p a s s e s th rough a maximum a t o r n e a r room tem pera tu re and d e ­ c re a s e s rap id ly a s th e tem pera tu re is lo w e re d . Some of th e s e com­ pounds have anom alous m agne tic p ro p e rtie s a t low tem p e ra tu re , bu t a p p ea r to be normal a t or n e a r room tem p e ra tu re . The in te ra c t io n b e ­ tw een d o rb ita ls of copper(II) ion s and th e n a tu re of th e lig an d s are re s p o n s ib le for th e m agn itude o f th is subnorm al b eh av io r . The la rg e overlap o f th e 3d o rb ita ls b e tw een th e copper(II) io n s in th e com plex a s w e ll a s the h igh te n d en cy o f the lig an d for coo rd in a tion w ill s ta b i l iz e th e d im eric s tru c tu re o f th e com p lex . S im ilarly th e fo rm ation of the d im eric compound in o rg an ic so lv en ts su ch a s a lc o h o l , e th e r , e tc . is more favo rab le th an in aqueou s so lu tio n . The d im eric s tru c tu re is d e ­ s tro y ed in w a te r , re s u lt in g in m onomeric hyd ra ted io n s . This is due to th e s tro ng e r coo rd in a tion a b il i ty o f w a te r compared w ith th a t of o rg an ic m o le c u le s . 31,8-NAPHTHYRIDINES'AND THEIR COMPLEXES: — The compound 1 ,8 -naph thy rid in e is an a rom atic m o lecu le (F ig . I) hav ing one un shared p a ir o f e le c tro n s on e a ch n itrog en and is sym bo lized th roughou t th is th e s i s a s "NN" for s im p lic ity . In n aph thy rid in e m o lecu le s th e p a irs o f e le c tro n s in th e nonbond ing a tom ic o rb ita ls o f the n itro g en s a re re sp o n ­ s ib le for th e ir b a s ic p ro p e r t ie s , s in c e ove rlap o f th is o r b i t a l , a s a Lew is b a s e , w ith an o rb ita l o f a Lew is a c id w ill re s u l t in a bond . Sub­ s titu tio n , o f two m ethy l g roups in 1 ,8 -naph thy rid in e "dmNN" would be ex p ec te d to in c re a s e th e b a s ic i ty o f th e s u b s t i tu te d m o lecu le a s is o b ­ se rv ed in 1 ,1 0 -p h en an th ro lin e . The b a s ic i ty o f th e p a ren t p h en an th ro - Iin e m o lecu le is low er com pared to th e 2,9-d im e thy l s u b s t i tu te d d e r iv a ­ t iv e . The pKa v a lu e s for some of th e n itrog en h e te ro cy c le s a re l i s te d in Table I , bu t the v a lu e o f pKQ for 1 ,8 -naph thy rid in e h a s n o t been repo rted in th e l i te r a tu re . In Table I , th e pKa v a lu e s o f d iffe ren t a rom atic am ines a re com pared in w h ich th e Ka v a lu e s a re th e d is s o c ia t io n con ­ s ta n ts o f p ro tona ted ammonium ion s a t 2 5°C in w a te r . Table I Compound Ref. 1,10 -p h en an th ro lin e 4.86 (13) 2 ,7 -d im e th y l-1 ,8 -n aph th y rid in e 2,9-d im e th y l-1,10 -p h en an th ro lin e 4.50 6.17 (13) (13) Pyrid ine (14)5.18 4j— N 1,10 -P h en an th ro lin e "phen" "dmp" 1 ,8 -N aph thy rid ine 2 ,7 -D im e th y l- l,8 -n ap h th y rid in e "NN" "dmNN" OUO 2 ,2 '-B ipy rid ine "b ipy" H e te ro cy c lic m o lecu le s c o n ta in in g two n itrogen a to m s . F igure I 5The compound 1,8-n ap h th y rid in e w as p repa red by Koller (15) and by A lbert (16) by a m u lt i- s te p seq u en ce s ta r t in g w ith m e th y l-2 - am in o n ic o tin a te . A llen (17) repo rted th e s y n th e s is o f 1 ,8 -naph thy rid in e u s in g 2 -am inopy rid in e a s th e s ta r t in g m a te r ia l . The s y n th e s is o f 2 ,7- d ic h lo ro -4 -m e th y l-1 ,8 -n a p h th y r id in e from 2 ,5 -d iam inopy rid in e w as re ­ po rted by S iede (18) in 1926. O ch ia i and M iyak i (19) repo rted a c a ta ly t ic hyd rogena tion schem e for c o nv e rs io n of 2 ,7 -d ic h lo ro -4 -m e th y l-1,8- n aph th y rid in e to 4 -m e th y l- l ,8 -n a p h th y r id in e . In 19 64 th e sy n th e s is o f 2- am in o -7-h y d ro x y -1,8-n ap h th y rid in e from 2 ,6 -d iam inopy rid in e w as re ­ po rted (20). Enwall (21) s y n th e s iz e d 1 ,8 -naph thy rid ine and i t s 4 -m ethy l d e r iv a tiv e by a fo u r -s te p s y n th e s is u s in g 2 ,6 -d iam inopy rid in e . All th e s e p rev io u s sy n th e s e s w h ich requ ire a m u lt i- s te p sy n th e ­ s is p ro ceed in a low y ie ld .. P aud le r and K ress (22, 23) repo rted in 1967 a o n e - s te p s y n th e s is o f 1 ,8 -n aph thy rid in e . They ap p lied th e Skraup re a c tio n to 2 -am inopy rid in e u s ing m e ta -n itro b en z en e su lfo n ic ac id (su lfo -m ix ) a s th e o x id iz in g a g en t. The co n d en sa tio n o f 2 -am inopy rid in e em ploy ing su lfo -m ix and g ly ce ro l gave 1 ,8 -n aph thy rid in e in 30% y ie ld w he rea s the 2 -am in o -6 - m e thy ln aph thy rid in e re a c tio n w ith c ro tona ld ehyde and su lfo -m ix p ro ­ duced 2 ,7 -d im e th y l-1 ,8 -n aph th y rid in e in 17% y ie ld . The f i r s t t r a n s i t io n m eta l com plex w ith 1 ,8 -naph thy rid in e w as sy n th e s iz e d and i t s s tru c tu re de te rm ined by X -ray d iff ra c tio n by Enwall (24) in th is la b o ra to ry . Enwall (21) is o la te d C u tN N ^C ^ and 6C u tN N ^B fg . The former w as a g reen c ry s ta l l in e s u b s ta n c e and the l a t t e r an o range compound w ith a d iso rd e red c ry s ta l s t r u c tu r e . Both com pounds w ere c ry s ta l l iz e d ou t o f aqueou s so lu tio n a n d .th e ch lo ride com plex w as shown to have a c is squ a re p la n a r s t r u c tu r e . N aph thy ri- d ine is c o o rd in a ted th rough one o f i t s n itro g en s ; the uncoo rd in a ted n itro g en s l ie be low and above th e p lan e o f th e com plex . / \ Cl Cl Bis( 1,8 -n aph thy rid in e ) copper(II) ch lo rid e F igure 2 The co p p e r-ch lo rid e d is ta n c e is 2 .2 5 $ , th e co p p e r-n itro g en d is ta n c e is 2 .0 2 $ , and th e c o p p e r-u n coo rd in a ted n itrog en d is ta n c e is 2 .76$ . The m agne tic s u s c e p t ib i l i ty m easu rem en t o f th e complex a t room tem peratu re show ed th a t i t had a norm al m agne tic moment o f 1.90 B. M . H end ricker and Reed (13) in 19 69 repo rted th e p rep a ra tio n and c h a ra c te r iz a tio n o f Group VIb m eta l c a rbony l com plexes w ith 72 ,7 -d im e th y l- l ,8 ~ n ap h th y r id in e „ From th e in fra red s p e c t r a , carbony l s tre tc h in g f r e q u e n c ie s , and th e ir fo rce c o n s ta n ts com pared w ith the five -m em bered ring n itrog en c h e la te s th ey conc luded th a t n aph thy rid in e is a s l ig h tly b e t te r rr-bonding lig an d . H end ricker (2 5) repo rted th e dia»lkyltin d ich lo rid e a d du c ts o f th is sam e lig an d and from th e ir in fra red and pmr sp e c tra he d e c id ed th a t the lig and forms a four-m em bered ring c h e la te w ith the c e n tra l m e ta l. H end ricker and Bodner (2 6) is o la te d m agnesium (II) , c a lc ium (II) , S tron tium (II), and barium (II) p e rch lo ra te com p lexes o f 1,8-n aph th y rid in e and i t s 2 ,7 -d im ethy l d e r iv a tiv e from anhydrous o rg an ic s o lu t io n s . Com­ p le x e s o f 1 ,8 -naph thy rid in e w ere h y d ra te d , bu t com p lexes o f 2,7- d im e th y l- l ,8 -n ap h th y r id in e were anhydrous ex cep t for th e m agnesium (II) com p lex . The so u rce o f th e w a te r in hyd ra ted compounds w as no t e x ­ p la in e d . From in fra red and p ro ton m agne tic re so n an c e s p e c tra th ey conc luded th a t a l l w ere c h e la te d w ith n aph thy rid in e th rough bo th n itro ­ g en s and th e p e rc h lo ra te s w ere a l l co o rd in a ted to th e c e n tra l m etal e x c e p t in M g fdm NN ^C lO ^g ' 3.5 HgO w here w a te r m o le cu le s were coo rd in a ted to th e m e ta l in s te a d of p e rc h lo ra te s . These sam e au tho rs (7,2 7) repo rted tra n s it io n m eta l com plexes o f iron(II) to z inc(II) a s w e ll a s cadm ium , m ercu ry , and s i lv e r w ith dmNN. Their anhydrous com p lexes had s to ich iom e try M(dmNN)3(C lO ^g ex cep t for m ercury and s i lv e r , w h ich w ere repo rted a s b is (dmNN) com p lex es . From th e in f ra re d , u l t r a v io le t , and v is ib le sp e c tra th ey a s s ig n e d 8 2+o c tah ed ra l geom etry to a l l th e ir t r is com pounds ex cep t Cu(dmNN)3 . They d id no t o b se rv e any d -d tra n s it io n for th e copper(II) com plex . The above au th o rs (1 ,2) a ls o repo rted e ig h t-c o o rd in a te tra n s it io n m eta l com p lexes o f NN w ith m etal io n s m ang an e se (II) , iro n ( I I ) , c o b a l t ( I I ) , n ic k e l ( I I ) , c o p p e r(I I ) , z in c ( I I ) , p a lla d ium (II) , and cadm ium (II). All com p lexes repo rted w ere anhydrous w ith s to ich iom etry M (NN)4(C lO 4)2 . Their powder pho tog raph d a ta show ed th a t com plexes o f m anganese(II) to copper(II) w ere a l l isom orph ic and th a t th e cadmium and z in c compounds w ere s im ila r . The s tru c tu re of th e Fe(NN)4(C lO 4)2 com plex h a s been de te rm ined (3) by X -ray d iffra c tio n m e th od s . The com plex has a d is to r te d d o d ecah ed ra l g eom etry . The s tru c tu re is shown in F igure 3. S tru c tu re o f te tra k is ( l ,8 -n a p h th y r id in e ) iro n (II )p e rc h lo ra te (3). F igure 3 9The iro n -n itro g en d is ta n c e v a r ie s from 2.18 to 2.75 A. Four n i tro g en s , one from each n aph thy rid in e m o le c u le , a re 2.18 to 2.25 8 d is ta n t from th e iron atom ; th e o th e r four n itro g en s a re a l l a t s ig n if ic a n tly g re a te r d i s ­ t a n c e s , 2.35 to 2 .75X, in d ic a tin g v e ry unsymm etrica l coo rd in a tio n o f th e n a p h th y r id in e s . C oo rd in a tion o f th e n aph thy rid in e m o fecu les th rough bo th n itro g en s is in c o n tra s t to th e m onoden ta te ly co o rd in a ted lig and in CufNMlgClg repo rted by Enwall (21). This r a is e s a number o f im portan t and in te re s t in g q u e s tio n s abou t how th e coo rd in a tion shou ld be d e ­ sc r ib ed in th e s e two ty p e s o f c om p le x e s . These q u e s tio n s w ill requ ire fu rth er s tu d y and have n o t been d e a l t w ith in th is t h e s i s . NITROGEN COMPLEXES OF COPPER (I):- In the c o u rse o f th is in - ■ v e s t ig a t io n a number o f copper(l) compounds w ere d is co v e red which proved to have u nu su a l p ro p e r tie s ; th e l i te ra tu re on re la te d compounds is summ arized h e r e . Copper(I) com p lexes w ith v a r io u s l ig a n d s , su ch a s 1,10- p h en an th ro lin e (p h en ) , .2,9-d im e th y l-1,10 -p h en an th ro lin e (dm p), 2,2' - b ip y rid in e (b ip y ) , d ia zo am in o b en z en e , d ia z e n e and s u b s t i tu te d d ia z e n e s have been s tu d ie d ,(6,2 8 ,29 ). T hese com p lexes ' h ave been p re ­ p a red e i th e r by redu c tio n o f copper(Il) s a l t s or by d ire c t re a c tio n of copper(I) s a l t s and an app rop ria te b a s e . P repara tion and c h a ra c te r iz a ­ tio n o f s e v e ra l copper(l) com p lexes o f m ono sub s titu ted d ia z e n e s (RN=NH) have b een repo rted (29). The c ry s ta l s tru c tu re s o f (CH3N=NCH3)C u2C l2 and (CgH5-N =N -N -C gH 5)2Cu2 have been 10 de term ined by X-^ray d iffra c tio n m ethods (30 ,31 ). The (CH3N=NCH3)C u2C l2 m o lecu le c o n s is ts o f in f in ite c h a in s o f copper and ch lo rin e a tom s w ith coppe r rough ly te tra h e d ra l ly co o rd in a ted by th ree ch lo rin e a tom s in th e ch a in and by a n itro g en lone p a ir from a d ia zen e m o lecu le (30). The (CgH3-N =N -N -C gH 3)2Cu2 m o lecu le e x is t s in a d im eric form in w hich th e d iazo am inob en zen e m o lecu le s a re lin k ed by n e a r ly l in e a r n i trd g en -c o p p e r-n itro g en coo rd in a tion to fprm an e ig h t- m embered ring w ith a c o p p e r-co p p e r d is ta n c e o f 2 .45^ (31). R eduction o f 1 ,1 0 -p h en an th ro lin e , o r 2 ,2 '-b ip y r id in e com plexes o f copper(Il) s a l t s in amm oniaca l so lu tio n w ith h y d ra z in e , sodium b is u l ­ f i t e , o r hydroxyl a m ine h a s been repo rted by T a rta rin i (6 ) . In some c a s e s th e copper(I) com p lexes w ere p rep a red d ire c tly from a m ixture o f copper(l) s a l t and th e lig a n d . The p rep a ra tio n o f C u (phen )2I , Cu(M py)I, C u(Phen)2ClO^ and Cu(M py)2ClO^ have been repo rted (6 ) , These com ­ p le x e s w ere conduc to rs in n itro b en zen e so lu tio n and th e ir sp e c tro p h o - tom e tric m easu rem en ts show ed th e p re s e n c e o f th e common ion CuL2 (L = ph en or b ip y ) . There w as a lso some ev id en ce for a sm all amount o f th e b ridged d im er o f 2,9-d im e th y l-1 ,1 0 -p h en an th ro lin e (dmp) in e q u i­ librium : ■ X 11 The fo llow ing re a c tio n h a s b een p ropo sed for thp p re s e n c e o f ion ic s p e c ie s in th e so lu tio n o f th is complex: 2 Cu(dmp)C l — > Cutdmp)* + C l" + CuCl “ lThe so lu tio n sp e c tra show ed abpo rp tipn maxima a t 21700 cm , in d ic a ­ tiv e o f Cutdmp)^ ion (6 ), P e tred is e t a l . (29) have a lso o b se rv ed s im ila r io n ic s p e c ie s w ith copper(I) com p lexes in th e so lu tio n and have is o la te d th e Cu(M py)^ ion a s i t s te tra p h en y lb o ra te s a l t . AIMS OF THIS RESEARCH: All p rev io u s s tu d ie s on t ra n s i t io n m eta l com plexes o f 1,10- p h en an th ro lin e and 2 ,2 '-b ip y r id in e (F igure I) have shown th a t th e se l ig a n d s co o rd in a te th rough th e ir two n itrog en atom s to th e c en tra l m e ta l. The [C u (phen )2X]X and [C u (b ip y )2X]X compound (X= Cl or Br) w ere shown to co n ta in f iv e -c o o rd in a te d copper(II) io n , w here th e m eta l h a s a tr ig o n a l pyram id g eom etry . W hen s a l t s o f an io n s o th e r than h a lid e s w ere u s e d , p e rc h lo ra te and n itr a te for in s ta n c e , th e lig and s w ere s t i l l found to c h e la te in th e sam e m anner, By c o n t r a s t , the repo rt o f th e s tru c tu re d e te rm in a tio n o f Cu(NN)2C l2 by X -ray d iff ra c tio n m e th ­ ods show ed th a t th e n a p h th y n d in e m o lecu le b eh av e s d iffe ren tly (21), Both h a lo g en s a re c o o rd in a ted to th e m eta l and th e n aph th y rid in e s are co o rd in a ted th rough on ly one o f th e n itro g en s . T h is w as th e on ly t ra n ed­ itio n m e ta l com plex w ith 1 ,8 -naph thy rid in e repo rted u n til 1968. This u n ex p ec ted p rope rty o f 1 ,8 -naph thy rid in e com pared w ith 12 1 ,10 -phenan th ro lin e and 2 ,2 '-b ip y r id in e s tim u la ted in te r e s t in s tu d ie s on t ra n s i t io n m eta l com p lexes co n ta in in g v a rio u s a n io n s . It h a s been po in ted ou t (7) th a t in 1 ,8 -naph thy rid in e and i t s 2 ,7 -d im ethy l d e riv a tiv e th e e le c tro n p a irs a re ex ten d ed in a p a ra l le l m anner and s e p a ra te d by app rox im a te ly 2.2 A, w he rea s in p h en an th ro lin e th e Icne n itrog en p a irs a re no t p a ra l le l bu t su b tend an ang le o f abou t 85° a t 2.00 R from the m e ta l c e n te r . This c h a r a c te r is t ic o f th e n aph thy rid in e m o le cu le , w h ich is s im ila r to th a t o f c a rb o x y la te io n , r e s u l ts in the fo rm ation o f p o ly ­ n u c le a r com p lexes w ith subnorm al m agne tic s u s c e p t ib i l i t i e s . Two su ch com p lexes have in d eed b een p rep a red during th is w ork . C om plexes of 2 .7 - d im e th y l-1 ,8 -n aph th y r id in e w ere o b ta in ed to s tu dy th e e f fe c t o f th e two m ethy l groups on coo rd in a tion c h a r a c te r is t ic s com pared w ith th e u n su b s ti tu te d l ig a n d . Is o la tio n o f m e ta l p e rch lo ra te com p lexes w ith 1 .8- n aph th y rid in e from aqueou s so lu tio n s w as c a rr ie d o u t .to de term ine th e e f fe c t o f w a te r o f hyd ra tion on coo rd in a tio n c h a r a c te r is t ic s of the lig and com pared w ith anhydrous compounds repo rted in th e li te ra tu re (1 ,2 ,3 ) . C om plexes o f m e ta l s a l t s o f n i t r a te , s u l f a te , and a c e ta te io n s w ere a ls o p rep a red to de te rm ine th e e f fe c t o f th e s e a n io n s on i ts c o ­ o rd in a tin g p ow e rs . F in a lly , four copper(I) com plexes o f 1 .8- n aph th y rid in e and i t s 2 ,7 -d im e th y l-1 ,8 -n aph th y rid in e w ere is o la te d in o rde r to in v e s t ig a te th e n a tu re o f an in co rre c tly repo rted com plex in th e l i te ra tu re (7 ). EX P E R IMENTAL ANALYTICAL TECHNIQUES The lig an d 1 ,8 -naph thy rid in e and i t s 2 ,7 -d im ethy l d e riv a tiv e w ere p rep a red by u s in g th e P aud le r and K ress p ro cedu res (21 ,22 ). R eagen t g rade ch em ica ls w ere u sed for a l l s y n th e s e s w ithou t fu rth e r p u r if ic a tio n . The copper(II) c o n cen tra tio n s w ere de te rm ined by a t i tr im e tr ic m ethod u s in g EDTA s tan d a rd so lu tio n (0.01-0.02 M) and f a s t Sulphone B lack F a s e n d -p o in t in d ic a to r (32). In some c a s e s w here th e e n d -p o in t w as n o t sharp th e io dom e tric m ethod (33), u s in g s ta n d a rd sodium th io ­ su lfa te so lu tio n (0.1 N), w as a p p lie d . Copper(I) c o n cen tra tio n s w ere de te rm ined by iodom etric ti tra tio n (33) o f an aqueou s so lu tio n o f the com plex w hich had b e en p rev io u s ly a ir o x id iz e d . M anganese(II) and z inc(II) c o n cen tra tio n s w ere e s tim a te d w ith s tan d a rd EDTA so lu tio n u s in g Eriochrome Black T a s th e e n d -p o in t in d ic a to r (32). C obalt(II) c o n cen tra tio n s w ere de te rm ined by EDTA titr a tio n w hich w as p re v io u s ly u sed in th is la b o ra to ry (34 ). N ickel(II) w as d e te rm ined by g rav im e tric m ethod u s in g d im e thy l- g lyoxim e a s p re c ip ita n t (32). S ilver(I) c o n cen tra tio n s w ere d e te rm ined by g rav im e tric p rocedu re and p re c ip i ta te s w ere w e ighed ou t a s s ilv e r(I) ch lo rid e (33). 14 Anion c o n cen tra tio n s in th e com p lexes w ere de te rm ined by an an ion exchange m ethod . A pyrex g la s s column which w as made in th is la b o ra to ry w as u sed in th is e s tim a tio n . The sh ape and th e m easu re ­ m en ts o f th is column a re shown in F igure 4 . The column w as f il led up to 15 cm w ith c a tio n ex ch ang e r e s in , Dowex 50W -X8, and w as reg en e r­ a ted w ith 6 M hyd roch lo ric a c id . In c a s e o f compounds con ta in ing s i lv e r , th e column w as re g en e ra ted w ith 6 M n itr ic a c id . The column w as w ash ed w ith d is t i l le d w a te r s e v e ra l tim es ; abou t 15-25 mg of the sam ple w as w e ighed e x a c t ly , th en w as d is so lv e d in 10 ml o f w a te r or an o rg an ic so lv en t and w as e lu te d th rough th e co lum n. After w ash ing th e 12 cm 11 12 cm v Schem atic d iagram of the io n -e x ch an g e co lum n . Figure 4 15 column w ith w a te r th re e t im e s , th e e lu te d so lu tio n s w ere c o lle c te d and t i t r a te d w ith s tan d a rd 0.05 M sodium hydrox ide to p h en o lp h th a le in end p o in t. F igure 4 show s th e sch em a tic d iagram of th e column be ing u sed in th is ex pe rim en t. Total ca rbon -hyd rog en a n a ly s e s w ere perform ed by C hem aly tics In c . , T em pe, A rizona. C onduc tan ce m easu rem en ts w ere o b ta in ed in m ethano l o r nitror- m ethane so lu tio n s o f th e com p lexes u s in g an In d u s tr ia l In s trum en ts M odel R C -16B2 co n d u c tan ce b r id g e . The c e l l w as c a l ib ra te d w ith a s tan d a rd p o ta ss ium ch lo rid e so lu tio n p rep a red w ith co ndu c tan ce w a te r . The in fra red sp e c tra (4000-250 cm "*■) w ere o b ta in ed w ith a Beckman In fra red S pec tropho tom ete r d oub le -b eam M odel IR -2 0 in p o ta ss ium b ro ­ m ide p e l l e t s . All sp e c tra w ere c a lib ra te d w ith p o ly s ty ren e film . D iffu se re f le c ta n c e s p e c tra (360 -800 nm) of th e com p lexes were o b ta in ed w ith a C ary M odel 1411 D iffu se R eflec tan ce by u s in g Type I i l lum in a tio n w ith in te g ra tin g sphere a tta chm en t a t W ash in g to n S ta te U n iv e rs ity , Pu llm an , W ash in g to n . All th e e le c tro n ic ab so rp tio n s p e c tra w ere m easu red in m ethanol o r a c e to n itr i le so lu tio n s o f th e compounds in m atched 10-mm or 1-mm qu a rtz c e l l s u s ing a C ary-14 reco rd ing sp ec tro p ho tom e te r. M agne tic s u s c e p t ib i l i t ie s w ere m easu red by th e Gouy method u s in g a M e ttle r a n a ly t ic a l b a la n c e , H a rv ey -W ells L-44V e lec trom agne t an d a M agnion M odel N o . HS425 pow er su p p ly . All s u s c e p t ib i l i t ie s 16 w ere de te rm ined a t room tem pera tu re e x c e p t th o se o f Cu(NN)Cl^ and Cu(NN)Brg w h ich w ere de te rm ined a t 196, 213.5, 250, 296, and 313°K. Four d iffe ren t f ie ld s tre n g th s w ere u sed in e ach s tu d y . The m easu re ­ m en ts a t g ach f ie ld w ere run in, t r ip l ic a te and th e av e rag e o f the !m easurements w as o b ta in e d . The d a ta w ere u sed to c a lc u la te the gram s u s c e p t ib i l i t ie s from th e equa tion : - 2 g . Aw 9 d .A .H 2 W here: g = a c c e le r a t io n o f g rav ity Aw = w e igh t change d = sam ple d e n s ity A = c r o s s - s e c t io n a l a re a o f Gouy tube H = m agne tic f ie ld s tre n g th M agne tic moments w ere o b ta in ed from th e equa tion : Ueff. = 2' 84 CD 6.34 Cu(py)2C l2 fo r com parison 50 18.6 a M = m e ta l. ^ A= an ion . c The c o n d u c tiv itie s w ere o b ta in ed in a b so lu te m ethanol so lu tio n s . c^ W ere f i r s t s y n th e s iz e d by Enwall (21). e The c o n d u c tiv itie s w ere o b ta in ed in DMF so lu tion s 21 . Cu(NN)^C0104)2 ' 4 H g O :- Aqueous so lu tio n s o f 0.37 g ( I mmol) o f cu p ric p e rc h lo ra te h ex ahyd ra te and 0.52 g (4 mmol) o f NN in 2 0 ml o f w a te r w ere m ixed and the. b lue p re c ip i ta te w as c o lle c te d in a s in te red g la s s fu n n e l . The b lu e s u b s ta n c e w as d ried and th en re c ry s ta l l iz e d from a m ix ture o f a c e to n e and a b so lu te m ethano l (1 :1 ). W hen th is com ­ pound w as r e c ry s ta l l iz e d from w a te r -a c e to n e m ixture (1:1) a b lue hyd ra ted c ry s ta l l in e compound w as o b ta in e d . Upon le a v in g th e s e c ry s ­ ta ls a t room tem pera tu re for s e v e ra l m inu te s a b lue pow der w as o b ta in e d . The a n a ly s e s o f th is anhyd rous compound a long w ith hyd ra ted c ry s ta ls a re g iv en in Tab le III . S ince th e hyd ra ted com plex w as no t s ta b le th e ca rb on -hyd rog en a n a ly s is w as n o t p o s s ib le . The w eigh t lo s s in th e compound w h ich w as de term ined by w eigh ing th e 'c r y s ta l s befo re and a f te r th e d ecom po s itio n w as c o n s is te n t w ith th e s e d e te rm in a tio n s . Mn(NN)4(C lO 4)2 * 4 H2O , Co(NN)4(C IO4)2 ' 4 H3O , Ni(NN)4(C lO 4)2 • 4 H2O , and Zn(NN)4(C lO 4)2: - S o lu tion s o f I mmol o f -M (C lO4)2 • x H2O (M = M n, C o , N i, and Zn) in 10 ml o f w a te r and 4 mmol o f NN in 5 ml o f w a te r w ere m ixed in a sm a ll Petri d is h . The so lu tio n s w ere k ep t a t room tem pera tu re p a r t ia l ly covered u n til th e c ry s ta l l iz a t io n w as com p le ted . The w e ll-fo rm ed c ry s ta ls w ere c o lle c te d in a s in te red g la s s funnel and a ir d r ie d . The compounds w ere r e c ry s ta l l iz e d from th e ir aqu eou s so lu tio n s by s im ila r p ro cedu re and w ere a n a ly z e d imme­ d ia te ly a f te r i s o la t io n . These hyd ra ted compounds w ere no t s ta b le in 2 . PERCHLORATE COMPLEXES; 22 a i r , th e lo s s o f th e w a te r o f h yd ra tion w as o b se rv ed g rad u a lly even a t room tem p e ra tu re . Zn(NN)2(C lC ) ^ ' 4 H2O : - To a so lu tio n o f 0.2 64 g (Imm ol) o f z in c(Il) p e rc h lo ra te h ex ahyd ra te in 5 ml o f w a te r 0,2 6 g (2 mmol) o f NN w as added and k ep t in a cham ber co n ta in in g a b so lu te m e th ano l. W hite la th -fo rm c ry s ta ls w ere o b ta in ed upon d iffu s io n w hich w ere c o lle c te d m anua lly on a f i l te r p ap e r and d ried o v e r ca lc ium c h lo r id e . Ag(NN)ClO^: — A so lu tio n o f 0.13 g ( I mmol) o f NN in 10 ml o f warm w a te r w as added to a ho t so lu tio n o f 0.207 g (I mmol) o f s ilv e r(l) p e r­ c h lo ra te in 50 ml o f w a te r . The so lu tio n w as a llow ed to coo l s low ly u n til th e c ry s ta l l iz a t io n w as com p le ted . The n eed le -fo rm c ry s ta ls w ere c o l le c te d , w ash ed w ith w a te r fo llow ed by a c e to n e , and d ried over ca lc ium c h lo r id e . The com plex w as re c ry s ta l l iz e d from ho t w a te r and d ried a s a b ov e . Table III Mn(NN)4(ClO4) Co(NN)4(C lO 4) Ni(NN)4C lO 4) 2 Cu(NN)4(C lO 4) Zn(NN)2(C lO 4) Co(NN)4(C lO 4) Cu(NN)4(C lO 4) Zn(NN)4(C lO 4), Ag(NN)ClO4 a M= m e ta l. ^ c o n d u c tiv it ie s PERCHLORATE COMPOUNDS C onduc- t iv i ty i / 0 O a lC Q • X / / 0 I o u r iQ \ Color A (molar) C oncn . C H Ma Ab - C H M A cm^ mho M xlO 4 2 ' 41iZ0 6.49 23.50 6.41 23.60 Yellow T9 7C 8.36 2 ' 4 ^ 0 6.23 23.38 6.29 23.15 Pink 207d 2.70 • 4 H9O 45.20. 3.79 6.90 23.39 44.66 3.55 6.78 23.28 B lue- 181d . 5.83 g reen 2 "4H2 ° ■ 7.43 23.26 7.51 23.12 Blue 2 14d 3.23 2 - 4K2O 32.21 3.38 10.96 33.34 32.12 3.05 11.18 33.72 W hite 208° 7.14 e 2 49.38 3.11 7.57 25.55 49.37 2.92 7.53 25.79 Pink 198° 8.92 e 2 49.08 3.09 8.11 25.40 48.79 2.82 8.18 25.60 Blue 206° 5.13 e 8.33 25.34 8.30 25.27 W hite 203° 4.28 31.9 6 29.47 31.75 29.51 W hite 102d . 2.14 c dA.= an io n . The c o n d u c tiv it ie s w ere o b ta in ed in n itrom ethane s o lu t io n s . The w ere o b ta in ed in a b so lu te m ethano l s o lu t io n s . e P rev iou s ly repo rted ( I ) . 24 3, NITRATE COMPLEXES: Co(NN)4 (NO3)2 * 6 H2O , N i(NN)3(NO3)2 * 4 H3O , and Zn(NN)4(NO3)3 ' 6 H3O: — So lu tion s o f I mmol o f M(NO3)3 ' 6 H3O (M = C o , N i , o r Zn) in 10 ml o f w a te r and 0.521 g (4 mmol) o f NN in 5 ml o f w a te r w ere m ixed and k ep t in a p a r t ia l ly open Petri d ish a t room tem per­ a tu re u n til th e c ry s ta l l iz a t io n w as com p le ted . The c ry s ta ls w ere c o l le c te d , w ash ed w ith 95% e th ano l and d ried over ca lc ium ch lo rid e in a d e s ic c a to r . The compounds w ere r e c ry s ta l l iz e d from th e ir aqueous so lu tio n s by a s im ila r p ro c e d u re . ' T hese compounds w ere no t s ta b le a t room tem p e ra tu re , th e w a te r o f hyd ra tion be ing lo s t upon s tand in g in a ir o r ove r ca lc ium ch lo rid e . Mn(NN)3(NO3)3: — C omm erc ia lly a v a ila b le 50% m anganese n i tr a te s o lu t io n , 5 m l, w as m ixed w ith 0.26 g (2 mmol) o f NN in a Petri d ish and w as k ep t covered in a da rk p la c e for abou t one w eek . The y e llow w e ll-fo rm ed c ry s ta ls w ere s e p a ra te d m anually on a f i l te r p aper and w ere w ashed w ith ch lo ro fo rm . The c ry s ta ls w ere k ep t in a c lo sed v ia l covered w ith b la ck p ap e r to p ro te c t th e c ry s ta ls from decom pos i­ t io n , and k ep t in a d e s ic c a to r . This compound w as h y g ro scop ic and l ig h t s e n s i t iv e . W hen so lu tio n o f th e compound w as ex p o sed to the l ig h t a b la ck p r e c ip i ta te , no t ve ry so lu b le in ino rg an ic a c i d s , w as ob ­ ta in e d . No id e n tif ic a t io n o f th is b la ck su b s ta n c e w as m ade. Cu(NN)2 ^g(NO3)3 and Cu(NN)2(NO3) 2: - S o lu tion s o f 0.296 g (I mmol) o f cu p ric n itr a te h exahyd ra te in 10 ml o f w a te r and 0.39 g 25 (3 mmol) o f N N in 5 ml o f w a te r were m ixed and k ep t in a p a r t i a l ly cov ­ e red Petri d i s h . Upon s low ev apo ra t ion o f the so lu tion a t room tem per­ a tu re , b lue c ry s ta l s were i s o la t e d a f te r a few d a y s . The c ry s ta l s were c o l le c te d by f i l t r a t i o n , w a sh ed w ith a sm all volume o f ch lo ro fo rm , and a i r d r ie d . Further r e c ry s ta l l i z a t io n o f the compound from i t s aqueous so lu t io n w as ca r r ied ou t by the same method . The compound was d ried over c a lc ium ch lo r id e and a n a ly z ed a s CufNNOg ^^(NOg)^ . When 0.2 g o f th i s complex w as d i s so lv e d in 30 ml o f a b so lu te m ethano l con ta in ing 10 ml o f 2,2 1 -d im ethoxyp ropane and w as re fluxed for 8 hours a b lue s u b ­ s ta n c e w as o b ta in e d . This compound w as c o l le c te d by f i l t r a t io n , w a sh ed w ith ch loroform , and dried ove r ca lc ium ch lo r id e , The s to i ­ ch iom etry of the complex w as proved by i t s e lem en ta l a n a ly s e s as Cu(NN^(NC)3)2 . This l a t t e r b is complex w as a l s o p repa red by d i s s o lv ­ ing an app rop r ia te ra t io o f the cup r ic n i t r a te and NN in dry methanol by a s im i la r m ethod . Co(NN)2(NO3)2 = — A so lu t io n o f 0.291 g ( I mmol) o f cobalt(II) n i t r a te h ex ahyd ra te in 10 ml o f a b so lu te e th ano l w as m ixed w ith 0.26 g (2 mmol) of NN in a 25 -m l b e ak e r . This so lu t ion w as k ep t in a c lo sed chamber for a few day s un t i l the p ink c ry s ta l s were i s o l a t e d . The c ry s ­ ta l s were c o l le c te d m anua l ly on a f i l te r p ap e r and d ried ove r ca lc ium c h lo r id e . This anhydrous s u b s ta n c e w as no t s ta b le and i t abso rbed w a te r from th e a tm osphere upon s tand ing in a i r . The rep roduc ib i l i ty of th is b is compound w as poo r and m os t o f th e time i t w as i s o la t e d w ith 26 d if fe ren t numbers o f hydra tion w a te r „ The hyd ra tion number v a r ied w ith the s o lv en t impurity §s w e ll a s the pe riod of time i t w as k ep t in s o lu ­ tion during the c ry s ta l l i z a t io n . Ag(NN)NO3: — A so lu t io n of 0.17 g (Immol) of AgNO3 in 50 ml of w a te r w as mixed w ith 0.13 g ( I mmol) o f NN in 10 ml o f w a te r . The white p re c ip i ta te w as c o l le c te d by f i l t r a t io n , w a sh ed w ith a c e t o n e , and a ir d r ied . This wh ite s u b s ta n c e w as d i s so lv e d in a su f f ic ie n t amount o f hot w a te r and a l low ed to coo l s low ly . The wh ite n e ed le s w ere c o l le c te d on a s in te red g la s s funne l and w a sh ed w ith a few m il l i l i te r s o f 95% e th an o l . The c ry s ta l s were a i r d ried and k ep t in a d e s ic c a to r over ca lc ium ch lo r id e . Table IV Mn(NN)2(NO3)2 Co(NN)2(NO3)2 OLEN N F2N A 3)2 Cu(NN)2 16(NO; N i(NN)2(NO3) 2 Co(NN)4(NO3) 2 Zn(NN)4(NO3)2 * Ag(NN)NO3 a M= m e ta l . ^ ^ NITRATE COMPOUNDS Conduc- / % C a lcd .- \ ( % Found Color LXVityw A (molar) C on cn . C N Ma Ab C H M A cm^ mho M x lO 4 12.51 28.23 12.77 28.09 Yellow 182 6.33 13.30 27.98 13.08 2 7.81 Pink 187 14.32 42.91 2.70 14.19 27.68 42.99 2.62 14.34 2 7.99 Blue 152 13.17 1^ 2 44.35 2.79 13.53 26.40 43.96 2.76 13.64 26.52 Blue 136 12.22 4H20 37.31 3.91 11.40 24.08 37.64 3.56 11.31 23.92 Blue- 185 8.97 green GH2O 47.35 4.47 7.26 15.2 8 47.34 4.43 7.58 15.57 Pink 208 7.14 GH2O 46.98 4.44 7.99 15.16 47.33 4.2 5 8.22 15.39 White 174 11.56 35.95 20.67 35.72 20.88 White 30 21.73 L- an io n . All the c o ndu c t iv i t ie s were ob ta in ed in a b so lu te methanol s o lu t i o n s . 28 4 . COPPER(I) COMPLEXES: Cu^(NN)Clg and CugWmNN)ClgZ-T To a so lu t ipn o f 0.198 g ( I mmol) o f CuCl in 40 ml o f warm a c e to n i t r i le 0.065 g (0.5 mmol) of NN or 0.079 g (0.5 mmol) o f dmNN in 10 ml o f a c e to n i t r i le w as a d d ed . The o range p re c ip i ta te w as c o l le c te d by f i l t r a t io n , w ashed w ith ab so lu te ■ m e th ano l , and a i r d r ie d . These compounds were po t s o lu b le in most o rd ina ry o rgan ic s o lv e n t s . Aqueous so lu tions , o f th e s e compounds were u n s ta b le in a i r and the copper(I) w as a i r ox id iz ed to a g reen copper(II) s p e c i e s . The p rep a ra t io n o f th e s e com p lexes under n i trog en a tm osphere gave pure p roduc ts w h ich were u s ed w ithou t any fu r ther p u r if ic a t io n . Cu(NN)ClO^z— To a so lu tion o f 0.1 g o f Cu(NN)^(C10^)g , in 30 ml of a b so lu te m e th ano l , 10 ml o f 2,21 -d im ethoxyp ropane w as added . This s o lu t io n w as re f luxed for four hours and 0.3 g o f cup ric p e rch lo ra te h exahyd ra te w as a d d e d . After re f lux ing th i s so lu tion for 12 hours i t w as c o n cen tra te d w ith warm ing under reduced p re s su re to o n e -h a l f the v o l ­ ume and k ep t under n i trogen in a chamber con ta in ing a b e ak e r o f sodium hydrox ide p e l l e t s . The o range c ry s ta l s were c o l le c te d by f i l t ra t io n , w a sh ed w ith ch lo ro fo rm , and dried ove r ca lc ium Chloride . The com­ pound w as r e c ry s t a l l i z e d from nitromethane so lu tion by a s im ila r m ethod . Cp(dmNN)2ClO4Z - A so lu t io n o f 0.14 g (0.42 mmol) o f cppric p e r ­ ch lo ra te h exahyd ra te in 40 ml o f a b so lu te p ie thanol apd IO ml o f 2 ,2 '- d im ethoxypropane w as re f luxed for s ix hours fo llowed by th e add it ion o f 0.158 g (I mmol) o f dmNN. After re f lpx ing for 18 hours th e l ig h t brown 29 so lu t io n w as a l low ed to coo l s low ly . The brown n e ed le s were c o l le c te d by f i l t ra t io n and. were r e c ry s ta l l i z e d from ab so lu te m e thano l or n i t ro - m e th a n e . The p roduc t w as w ashed w ith chloroform and d r ied over ca lc ium ch lo ride . Table V COPPER(I) COMPOUNDS Conduc- /----------% C a l c d . - - r % Round tiv i tyColor A (molar) C on cn . C H Ma AD C H M A Cm^ mho M x lO 4 Cu2(NN)Ol2 29.28 1.85 38.73 29.36 1.62 38.83 Orange - 132^ 3.81 Cu2(dmNN)Cl2 33.72 2.83 35.68 34.45 2.85 35.39 Orange 122^ 9.09 Cu(NN)ClO^ 32.78 2.06 21.67 32.67 2.00 21.36 Orange IO ld 15.62 Cu(dmNN)2C104 50.10 4.2 0 13.25 28.74 50.20 4.25 12.98 20.69 Brown 112® 0.84 a M = m e ta l . ^A= a n io n . C,c*, e The c o n d u c t iv i t ie s were ob ta in ed in; a c e to n i t r i le ( c ) , n i t ro - methan ( d ) , and a b so lu te m ethanol {e) s o lu t i o n s . RESULTS AND DISCUSSION PART I — HALIDE COMPLEXES: The a n a ly t ic a l and p h y s ic a l d a ta for h a l id e com p lexes a re r e ­ ported in Table II . A ttempts to de te rm ine the m elting po in t of the com p lexes were u n s u c c e s s fu l due to decom pos it ion o f the compounds a t tem pe ra tu res o f abou t 240 °C . The compounds a re a l l s t a b le on exposu re to l ig h t and a i r e x c e p t CuCdmNN^Cl2 , w h ich g radua lly c h ang e s from blue to brown upon s tand ing in s u n l ig h t for two w e e k s . The m agne t ic s u s c e p t ib i l i t i e s o f a l l copper(II) com p lexes were de te rm ined and from the ob se rv ed s u s c e p t ib i l i t i e s th e .m agn e t ic moments p e r copper atom were e v a lu a te d . The-magnetic moments o f a l l com­ p le x e s (Table VI), a p a r t from m on o -c om p le x e s , l ie in th e range 1.99-2.01 B .M . The normal m agne t ic moment a s s o c i a t e d w ith copper(II) compounds is 1.8-2.2 B .M . (12). From th is i t i s conc luded th a t the copper(II) com p lexes o f NN and dmNN w ith m agnetic moments of 1.99- 2.01 B .M . a re m ononuclear; on the o th e r h an d , th e Cu(NN)C l2 and Cu(NN)Br2 complexes w ith room tem pera tu re m agne t ic moments of 1.69 B .M . and 1.59 B .M . re s p e c t iv e ly a re s im ila r to th o se o f copper(II) c a rb o xy la te s (12). As no ted in the in t ro d u c t io n , th e s e l a t t e r compounds exh ib i t subnormal m agne t ic m om en ts , and have a maximum in a p lo t o f molar m agne t ic s u s c e p t ib i l i ty v e rsu s tem pe ra tu re . The m agne t ic s u s ­ c e p t ib i l i t i e s o f th e Cu(NN)C l2 and Cu(NN)Br2 compounds were d e te r ­ m ined a t s ev e ra l d if fe ren t tem pe ra tu res and i t w as found th a t they were 32 MAGNETIC SUSCEPTIBILITY OF DATA OF HALIDE COMPLEXES Table VI Compound D iam agne tic Co rrec tion , n6c . g . s . u . x 10 C o rr . H T x106 c . g . s . u . T , °K ^eff. B .M . Cu(NN)2C l2 193 1704 296 2.01 Cu(NN)2Br2 217 1670 296 1.99 Co(NN)2C l2 193- 8149 298 4.40 Cu(dmNN)2Br2 2 63 1670 296 1.99 Cu(NN)C l2 120 . 1107 326 1.70 1153 313 1.70 1201 297 1.69 1376 250 1.66 1497 213.5 1.60 1530 196 1.55 Cu(NN)Br2 143 1081 326 1.68 1035 313 1.61 1066 296 1.59 1109 250 1.49 1163 312.5 1.41 1110 196 1.32 33 tem pera tu re d ep end en t and s im ila r to copper(II) a c e ta t e monohydrate (Table VI). In Figure 5 , p lo ts o f molar m agne t ic s u s c e p t ib i l i t i e s v e rsu s tem pera tu re a re shown . The Cu(NN)Br2 h a s a maximum a t a b o u t 2 15°K and the maximum for Cu(NN)C l2 i s b e low 19 6°K. The Cu2(CHgCOO)^ ' 2 H2O curve is shown for c om pa r iso n , w ith maximum a t abou t 260°K. These d a ta s u g g e s t th a t th e s e two comp lexes a re b ridged b in u c le a r m o le c u l e s . - S ince h a l id e b r idged copper(II) compounds are v e ry common, and th is subnormal m agne t ic b eh av io r w as ob se rv ed on ly in h a l id e com­ p le x e s i t is p o s s ib le th a t th e s e m ight be ha lid e b ridged d im e rs . It has been repo r ted in the l i te ra tu re th a t copper(II) compounds con ta in ing h a l id e b r idges do no t e x h ib i t subnormal m agne t ic p rope r t ie s , a t room tem pe ra tu re (36). Thus i t s eem s l ik e ly th a t 1 ,8 -naph thy rid ine m o lecu les a re b ridged a c ro s s the two copper a toms in Cu(NN)Cl2 and Cu(NN)Br2 com pound s . M o lecu la r w e igh ts would be u se fu l on confirm ing the above h y po th e s is but the sp a r ing s o lu b i l i t i e s o f th e copper(II) h a l id e com­ pounds p rev en ted the de te rm ina tion o f m o lecu la r w e ig h t s . By com parison of X -ray powder p h o to g ra p h s , i t w a s found th a t the c ry s ta l s o f Cu(NN)C l2 and Cu(NN)Br2 were isomorphous w h ich w ill be d i s c u s s e d in the fo llow ing p a r a g r a p h s . The comparison of Cu(NN)Cl2 and Cu(NN)Br2 in fra red sp e c tra showed th a t bo th were s im ila r in the reg ion 4000-300 cm \ The l igand x 10 34 iooo r I C u2(CH3COO)4 • 2 H2O . II C u (CgH6N2)Bi2 III C u (C fiHfiN9)C l9 Figure 5. M agne tic s u s c e p t ib i l i t i e s o f th e subnormal Copper(II) c om p le x e s . F igune 6. 36 mode for 1,8-n aph thy r id in e have b een a s s ig n e d and reco rded in the range 1700-650 cm * by Armarego e t a h (37) „ As would be e x p e c te d , the l ig and in fra red spec trum a l te re d on coo rd in a t io n . In Table V II, the l ig and modes w h ich sh if t s ig n i f ic a n t ly upon coo rd ina tion and the p a ren t l ig and v ib ra t io n s a re l i s t e d . Prev ious s tu d ie s (38) on complexes con ta in ing m e ta l -h a lo g en bonds in d ic a te th a t the m e ta l -c h lo r in e s t re tch in g f requenc ie s occu r b e - tw een 350-250 cm and m e ta l-b rom ine f r equenc ie s from be low - I 250-200 cm . The b ridged c o pp e r -ch lo r in e and te rm ina l copp e r -ch lo r in e s t r e tc h in g v ib ra t io n s have b een o b se rv ed a t 311 cm and 32 6-330 cm re s p e c t iv e ly (39 ,40 ) . The te rm ina l c o p p e r -ch lo r in e s t re tc h in g v ib ra ­ t io n s in CufpyjgClg and E t^N ^C uC l^ compounds have b e en reported a t 287 cm ^ and 2 68-2 89 cm ^ r e s p e c t iv e ly (41 ,42 ) . In Tab le VIII, the c o pp e r -ch lo r in e s t r e tc h in g f requenc ie s for b ridged and te rm ina l ch lo ride io n s , in some copper(II) complexes a re l i s t e d . The te rm ina l coppe r - ch lo r in e s t re tch in g frequency in Cu(NN)^Clg complex ( s e e Figure 8) - I occu rs a s a s in g le broad band w ith th e ab so rp t ion maximum a t 282 cm wh ich i s in good ag reem en t w ith th e v a lu e s reported for Cu(Py)^Clg and (E t^N)gCuCl^ com pound s . In Cu(NN)Clg the sh ape o f th i s band is qu ite d if fe ren t and sh if ts to h ighe r f requency ( s e e Figure 8) w h ich in d ic a te s d i f fe ren t c o p p e r -ch lo r in e bond(s) compared w ith the Cu(NN)gClg com­ p lex con ta in in g two te rm ina l ch lo r ide io n s (Figure 2). The coppe r - bromine s t re tc h in g f requenc ie s were no t ob se rv ed in th is s tu dy which Table VII SELECTED INFRARED ABSORPTIONS (400-2 50 CM X) OF HALIDE COMPLEXES* Band NN Cu(NN)Cl2 Cu(NN)Br2 Cu(NN)2C l2 Cu(NN)2Br2 Co(NN)2Cl I 1555 v s 1572 s 1570 m 1580 s 1570 s 1565 s II 1492 vs 1510 vs 1510 vs 1495 vs 1502 vs 1502 vs III 1360 w, sh 1350 s 1350 s * * # * * * » * IV 1288 s 1240 m 1240 w 1236 vs 1240 m 1234 m V • • • » • • « • » # # * ft ft ft C 1147 m 1145 s VI 1128 vs 1138 s 1138 m 1136 s 1128 s 1128 s VII 1045 m 1082 m 1082 w. 1057 m 1062 s 1063 s VIII 1026 s 1055 vw 1056 vw 1031 m 1035 m 1035 m IX 9 69 v s ' 982 m 981 w ■ 9 68 vw 970 vw 970 vw X 953 vw 9 65 w 9 63 vw 9 58 vw 9 60 vw 957 w ' XI 835 vs 848 vw 847 s 842 s 7sh 845 s 7sh 840 vs XII 809 vs 842 s 842 s 835 vs 840 vs 835 s 7sl XIII 773 m ,s h 830 m 834 m ,s h 800 vs 800 vs 803 vs XIV 760 vs 790 vs 790 v s 780 vs 785 vs 785 vs XV 600 w 640 vw 638 vw 622 m 630 w 627 in XVI 402 m 437 m 435 vw 420 m 427 w 426 m XVII 300 vw 300 s, br 300 vw 282 v s , br 275 w, sh 310 s XVIII 2 72 vw 290 m 2 80 vw7sh * # * * 2 65 w, sh 285 m XIX 245 s 245 s 257 m * The a s s ig nm en ts are: s, s trong ; v, very; m, medium; sh, shoulder; br, broad; w, weak 38 M icrons 5 5.5 6 6.5 7 7.5 8 9 10 11 12 14 16 18 20 25 30 40 2000 Figure 7. Infrared Spec tra of and CgHgNg T R A N S / 39 TT"'I... I O L I O YP R I O I D V— I" I - - I C u I C 0H - N0 I0 CI ‘ j " ! " ) • • • " j Figure 8 . Infrared Spec tra o f Cu(CgHgN2)C l2 and Cu (CgHgN2) 2C l2 . :E N T T K A N S l 40 Table VIII INFRARED ABSORPTIONS OF SOME Cu(II) COMPLEXES a |u, B. M. C u -C lb, CM”1 Cu(NN)2C l2 2.01 282 Cu(NN)C l2 1.-69 300, 290 C(PyO) C uC l2 ] 2C 0.59-1.06, 0.63 330 ,311 [ (S -CH 3PyO)CuC l2 ] 2 0.55, 0.97 320 [ (4 -C H 3PyO )CuC l2 ] 2 • 0.49, 0.52 327, 312 [(PyO)2CuCl2 ] 2 0.46, 0.63 310 ,280 (2 -C H 3PyO) 2 C uC l2 1.95 328 (S-CH3PyO)2CuCl2 . . . . 322 [2 ,6 - (CH3)2PyO J2CuCl2 1.91 319, 297 Cu3C l6 [4 -C l (q u inO ) ]2C 2.07 308, 290 CuC l2(4 -C l -P y )2G 1.83 294^ CuCl2(Py)2 . . . . 287 (Et4N )2CuC l46 289 s h , 268 a bReference 39. Commas s e p a ra te more th an one in fra red band . C PyO = py rid ine N -ox id e ; QuinO = quinoline N -ox ide ; Py = p y r id in e . ^ R e fe ren ce 42 . e Reference 42. 41 in d ic a te s th a t the b and s ob se rv ed a t 300(s ,br) cm * and 290(m) cm- '1' are c o pp e r -ch lo r in e s t r e tc h in g v ib ra t io n s o f Gu(NN)Clg complex . The re f le c ta n c e sp e c t r a of copper(II) h a l id e com p lexes of 1 ,8 -naph thy rid ine a re shown in Figure 9 and th e i r a b so rp t io n maxima are l i s t e d in Table IX. The d if fu se re f le c ta n c e sp e c t ra o f Cu(NN)Clg and Cu(NN)Brg a re s im ila r w ith ab so rp t ion maxima a t 13240 cm ^ and 13160 cm- ^ r e s p e c t iv e ly which is c o n s i s t e n t w ith the w eak e r l igand f ie ld s t re ng th o f bromide compared w ith c h lo r id e . From m agne t ic s u s c e p t ib i l i ty m ea su rem en ts . X -ray powder pho to ­ g r a p h s , a n d v i s ib le and unfrared s p e c t ra of Cu(NN)Xg (X= Cl or Br) th e re a re s e v e ra l p o s s ib le s t ru c tu re s which can be s u g g e s te d for th e s e c om p lex e s . Among a l l p o s s ib le s t ru c tu re s th e re is on ly one s tru c tu re which f i t s th e d a ta . In Figure 6-A , a d imer molecu le o f Cu(NN)Xg is shown in w h ich two naph thy rid ine m o lecu le s a re coo rd in a ted through two n i trogen s a c ro s s th e two Cu(II) io n s w ith two ha log en atoms form­ ing b r idges in the p lan e p e rp end icu la r to th e p lane of th e naph thy rid ine m o lecu le s and two te rm ina l h a logen s on e ach s id e of th e b in u c le a r com p lex . These two te rm ina l h a log en s may coo rd ina te to th e n e ighbo r­ ing m o lecu le s u n symm e tr ic a l ly , g iv ing r i s e to one sh o r t and one long c o pp e r -ch lo r in e bond d i s t a n c e . Figure 6 -B shows an a l te rn a t iv e p o s ­ s ib le s t ru c tu re in which copper a toms a re b ridged in p a i r s by two naph thy r id in e m o le cu le s w ith th e four h a l id e ions o ccupy ing te rm ina l p o s i t io n s . In F igure 6-B , both te rm ina l ch lo ride ions a re equ iv a len t RE LA TI VE I N TE N SI TY 42 ---- Cu(NN)Cl2 — Cu(NN)Br ----- Cu(NN)2Cl - - Cu(NN)9 Br, Il r \ \ 25000 cm1700012000 Figure 9 . D iffuse r e f le c ta n c e o f h a l id e complexes . 43 Table IX VISIBLE ABSORPTION SPECTRA OF HALIDE COMPLEXES (CM™1) C h a rg e - t r a n s fe r and l ig and bands d -d bands Cu(NN)Cl2 26800 , 21980 sh 14660 s h , 13240 Cu(NN)Br2 28400 , 21740 14490 s h , 13160 Cu(NN)2C l2 27030 sh 14800, 13330 sh Cu(NN)2Br2 28170 s h , 22470 sh 13000 Co(NN)2C l* 17180, 16750, 16390, 15950 * The spec trum w as o b ta in ed in n itrom ethane so lu t io n . and th e c o pp e r -ch lo r in e s t re tch in g v ib ra t io n s would a p p ea r a s a s in g le b and , a s is ob se rv ed in th e Cu(NN)2C l2 spec trum . The in frared v ib ra ­ tion f requ en c ie s o f c o p p e r -ch lo r in e s t re tc h in g bands in Cu(NN)Cl2 complex in d ic a te th a t the ch lo ride io n s a re no t e q u iv a len t and they p robab ly have d if fe ren t ty p e s of coo rd in a tion to the copper(II) ion . This i s in ag reem en t w ith th e s t ru c tu re 6-A w h ich con ta in s two d iffe ren t k ind s o f ch lo r in e s coo rd in a ted to the copper a tom . The s t ru c tu re 6-B co n ta in s on ly one k ind o f co pp e r -h a lo g en bond , w he rea s th e infrared spec trum seem s to c a l l for two . Cu(NN)2C l2 and Cu(NN)2Br2: - The m agnetic moments o f th e s e com p lexes (Table VI) in d ic a te th a t th e m o lecu les e x i s t a s mononuclear 44 s p e c i e s . The X -ray powder pho tog raphs showed d if fe ren ce s in d ic a t in g th a t th e s e com p lexes a re no t isom o rph ic . The in fra red spec trum of Cu(NN)2Br2 w as compared w ith th o se o f Cu(NN)2C l2 , Cu(NN)C l2 , and te t r a k is n i t r a te and p e rch lo ra te com p lexes which con ta in b id en ta te ly coo rd in a ted n aph thy r id in e in th e reg ion 4000-300 cm \ The l igand modes o f th e b is h a l id e com p lexes a re l i s t e d in Table VII. The band a t 1350 cm * which o ccu rs in Cu(NN)C l2 i s no t p re s en t in the C u(NN)gBr2 - I spec trum and a new band a t 1147cm h a s app ea red . The sp l i t t in g of - I - I - Ith e l ig and band a t 1128 cm in to two bands a t 1128 cm and 1145 cm has a l s o b een repo r ted (2 6) for dmNN complexes in w h ich 2 ,7 -d im e thy l- 1,8-n aph th y r id in e s were coo rd in a ted th rough both n i trogen s to the m eta l i o n s . The in fra red spec trum o f th e Cu(NN)2Br2 complex w as s im ila r to th e s p e c t ra o f the te t r a k is p e rch lo ra te complexes ( s e e Figure 3) in w h ich n ap h thy r id in e s were coo rd in a ted th rough bo th n i t rog en s to the m eta l ion . The sp l i t t in g o f th e l ig and band a t 1128 cm * w as no t ob ­ se rv ed in p e rch lo ra te complexes b e c a u s e th is reg ion o f the sp ec tra w a s covered by v e ry s trong and broad band of p e rch lo ra te an ion . The sp e c t r a o f p e rch lo ra te complexes were su p e r im po sab le , a p a r t from p e r ­ ch lo ra te and n i t r a te b a n d s , on sp e c t r a o f n i t r a te com p lexes in which the s p l i t t in g of th e 112 8 cm * l ig and band s w as o b se rv ed ( s e e Table XVIII). The ag reem en t o f the Cu(NN)2Br2 in frared spec trum w ith th o se of c h e la te d com p lexes s u g g e s t s th a t th e naph thy rid ine m o le cu le s a re c o ­ o rd in a ted th rough bo th n i trogen a tom s to th e m eta l ion . The 45 copper-b rom ine s t r e tc h in g f requenc ie s were no t o b se rv ed in th is s tudy s in c e th ey were beyond the range o f the in s trum en t a v a i l a b le to u s . This a l s o in d ic a te s th a t th e band o b se rv ed a t 282(vs,br) cm * in Cu(NN)^Clg is c o p p e r -ch lo r in e s t re tch in g v ib ra t ion s in c e i t w as not o b se rv ed in Cu(NN)2Brg complex . The re f le c ta n c e s p e c t ra of Cu(NN)gClg and Cu(NN)2Brg in the v i s ib le reg ion a re shown in Figure 9 and the ab so rp tion b and s a re l i s t e d in Table IX. The Cu(NN)2Clg spec trum co n ta in s a broad band w ith an i l l - d e f in e d maximum in th e reg ion 15000-13000 cm w he rea s the s p e c ­ trum of Cu(NN)2Br2 showed com para t iv e ly sharp band w ith ab so rp tion maximum a t 13000 cm ^ wh ich ag a in in d ic a te s th a t the g eom etr ie s o f the two complexes a re no t s im i la r . Above 2000 cm the ab so rp t io n r i s e s sh a rp ly due to charge t r a n s fe r and ligand bands ( s e e Figure 9 and Table IX). S eve ra l copper(II) compounds w ith d if fe ren t g eom etr ie s and v is ib le ab so rp t io n band(s) a re l i s t e d for comparison in Table X. The p o s i t io n of th e ab so rp t ion bands in copper(II) complexes v a r ie s g re a t ly w ith d if fe r ­ en t coo rd in a tion g eom e t r ie s . To a s s ig n a geometry to th e Cu(NN)2Br2 from i t s v i s ib le ab so rp t ion band is c le a r ly no t p o s s i b l e , bu t the s p e c ­ trum is s im ila r to th o se o f d is to r te d o c tah ed ra l c om p lex e s . The molar conduc t iv i ty o f th e Cu(NN)2Br2 in a b so lu te m ethanol so lu t io n (Table II) in d ic a te d th a t the complex w as no t io n ic and the in fra red spec trum su g ­ g e s te d coo rd ina tion o f the l ig and s th rough both n i t r o g e n s . Thus a 46 Table X ELECTRONIC ABSORPTION SPECTRA OF SOME Cu(II) HALIDES3 Compound Geometry V isib le Bands —I, cm C u (Dm q)C l^ d i s t . o c t . 18690 sh 14180 Cu(Dmq) Br^ d i s t . o c t . 14925 T ran s -C u (D pq )0C l0^ sq u . p la n a r 18690 14290 T ran s -C u (D pq )0Br0 squ . p lan a r 14925 Cu(Mq) % Clgb d is t . . o c t . 14700, Cu(Mq)2Br2 d i s t . o c t . 16130 Cu(Mpy)2C l20 ' te t ra gon a l 28000 12800 Cu(b ipy)2Br2G pyram idal 26700 . 12800 CuC l2 * 2 N H ^ d i s t . o c t . ' 14850 CuBr2 • 2 NHgd d i s t . o c t . 14800 CuC l2Py26 d i s t . oct.. 14500 Cu(4 -M eT )C l2f d i s t . o c t . 25600 13300 a Reference 44 . ^ Dmq= 2,3 -d im e thy lqu inoxa l in e ; Dpq= 2,3- d iph eny lqu inoxa lin e ; Mq = 2 -m e th y lq u in o x a l in e . C R eference 45 . R eference 46 . e R eferences 43, 47. ^4 -M e t= 4 -m e thy l th ia zo le ; re fe ren ce 48. 47 d is to r te d o c tah ed ra l geometry for the copper(li) ion su rrounded by four n i trogen s and two bromine atoms seem s l ik e ly . CufdmNNlgClg and C uCdmNN^B^ :— The in fra red sp e c t ra of the o l iv e -g re e n CuCdmNN^Brg and the b lue CuCdmNN^Clg were id en t ic a l . and a l s o were supe r im po sab le on the spec trum of the brown CuCdmNN^Clg w h ich w as ob ta in ed from decompos it ion o f the b lue d e ­ r iv a t iv e upon expo su re to su n l ig h t for two w e e k s . The l ig and modes which s h if t s ig n i f ic a n t ly upon coo rd ina tion and the free l ig and v ib ra ­ t io n s a re l i s t e d in Table XI. The a s s ig nm en t of the l ig and modes has b een repo rted in the l i te ra tu re (7). In th e sp e c t ra of t h e s e complexes the l ig and band a t 112 8 cm * w as no t o b se rv ed a f te r coo rd ina tion and - I on ly one s trong band a t 1147 cm w as p r e s e n t . This a p p ea ran ce of a s in g le band in the reg ion 1100-1200 cm is s im ila r to the s ing le band ob se rv ed a t 1136(s) cm * in Cu(NN)gClg in which n aph thy r id in e s were coo rd in a ted th rough one of th e n i trogen s to th e copper io n . This i s in c o n t r a s t to the in fra red sp e c t r a o f the dmNN complexes repo rted in the l i te ra tu re (2 6) in which n aph thy r id in e s were ch e la te d and showed two bands a t 1128 cm * and 1145 cm *. The in fra red ab so rp t ion bands were compared w ith th a t o f th e iron complex , Fe(dmNN)g(ClC^)g (7). The l ig and bands a t 847(vs), 805(vs), and 778(vs) cm \ wh ich a re s e n s i t iv e to coo rd in a tion and sh if t to 870(s), 853(s), and 803(vs) cm * r e sp e c t iv e ly in iron(II) com p lex , were o b se rv ed a s five bands a t 868(vs), 815(m, sh), 810(s), 803(vs), and 777(w) cm ^ (Table XI) in Cu(dmNN)g+ ha lid e 48 Table XI SELECTED INFRARED ABSORPTIONS (4000-2 50 CM ) OF Cu(dmNN)2X2 Band dmNN Cu(dmNN)2C l2 Cu(dmNN)2Br2 I 1532 m 1570 s 1567 s II 1360 w 1380 s- 1380 s III 1240 s , 1255 s 1253 s IV 1205 m 1220 m 122 0 m V 847 vs 868 vs 867 vs VI • • • « 815 m ,s h 816 m ,s h VII 805 vs 810 s ' 810 s VIII . • e • 803 v s 802 vs ■ IX 778 v s ' 777 w 777 w X 625 m 648 w 648 w XI O » • e 515 w 514 w XII 442 m 457 m ' 457 m XIII 345 m 353 vw 352 vw XIV 268 w 283 v s ,b r 2 80 s ,b r * The a s s ig nm en ts are: s, s trong; v s , v e ry strong; w, w eak ; vw, very- weak; m , medium; s h , shou lder; br, b road . 49 com p lex e s . All th e s e d a ta s u g g e s t th a t n aph thy r id ine s a re coo rd ina ted m onoden ta te ly to the copper ion in Cu(DmNN)^Clg and Cu(dmNN)2Br2 c om p le x e s . The X -ray powder pho tog raphs o f b lue Cu(dmNN)2C l2 , brown Cu(dmNN)2C l2 , and o l iv e -g re e n Cu(dmNN)2Br2 were a l l s im i la r and did no t show any s ig n i f ic a n t change s in th e in te n s i ty or p o s i t io n of the s p e c t r a l l i n e s , wh ich in d ic a te s th a t a l l compounds a re isom o rph ic , in good ag reem en t w ith the in fra red d a ta . The na tu re o f the co lo r change from b lue to brown upon exposu re to s u n l ig h t of the Cu(dmNN)2C l2 is a ve ry in te r e s t in g problem bu t h a s not b een in v e s t ig a te d in th is r e s e a rc h . The Cu(dmNN)2Br2 complex gave a m agne t ic moment of 1.99 B .M . s im i­ la r to the v a lu e s o b ta in ed for m ononuc lear copper(II) com p lexes (see Table VI). The spar ing s o lu b i l i t i e s of the above complexes in o rgan ic s o l ­ v en ts d id no t pe rm it v i s ib le sp e c t ra m e a su rem en ts . The molar conduc­ t iv i ty v a lu e s o f th e com p lexes in DMF so lu t io n s in d ic a ted th a t the com p lexes were no t io n ic . This s u g g e s t s coo rd ina tion o f th e ch loride and bromide ions to the copper io n s . From in fra red ab so rp t io n s p e c t r a , m agne t ic m om en ts , and X-ray powder d a ta i t is no t p o s s ib le to a s s ig n a c e r ta in geometry to the com­ p l e x e s , bu t a m o lecu la r model shows th a t the methyl g roups on the s u b s t i tu te d n aph thy r id ine m o lecu les would no t perm it formation o f a c is s q u a r e -p l a n a r geometry around the copper a tom . The model shows a 50 s e v e re ly h inde red s t ru c tu re for a c is com p lex , w he rea s th i s h indrance does no t p roh ib i t th e m o lecu le from forming a c is geometry in Cu(NN)£C ^ ; th e re fo re a t ra n s geometry is p red ic ted in 2 ,7-d imethy l s u b s t i tu te d n aph thy r id ine c om p lex e s . The d if fe rences in co lo r o f g reen Cu(dmNN)2Br2 from Cu(NN)2Br2 and the s im ila r i ty of the co lo r to the t r a n s -C u (py )2Br2 (green) in d ic a te s th a t the env ironment of th e copper(II) ion shou ld be s im ila r to th a t of the py rid ine complex , i . e . , t ran s geome­ try ra th e r than c i s . The Cu(dmNN)2C l2 (blue) a l s o has a d iffe ren t co lo r from th a t o f Cu(NN)2C l2 (green) and is s im ila r to t r a n s -C u (p y )2C l2 (g re en ish -b lu e ) wh ich a g a in s u g g e s t s a t ra n s geometry for the Cu(dmNN)2C l2 complex . These o b se rv a t io n s a re in good ag reem en t w ith the m o lecu la r model s u g g e s te d a b o v e . Co(NN)2C l2 = - The v i s ib le spec trum of Co(NN)2C l2 in n itrom eth - _1 ane so lu t io n showed four b road bands in th e reg ion 17000-15000 cm (Table IX) w ith molar a b so rp t iv i t ie s o f 3 50 -420 . This i s in good a g re e ­ ment w ith th o se repo rted for o the r te t r a h ed ra l cobalt(II) complexes (49). The ab so rp t ion bands repo r ted for te t r a h ed ra l te t raha lo coba lt( I I ) ions have b een repo rted in th e range 23000-15000 cm (50). The b lue com­ p le x is s ta b le in n itromethane. so lu tion , bu t no t in w a te r or a b so lu te m e thano l. After d is so lv in g the b lue compound in w a te r or ab so lu te m ethano l a p ink so lu tion , i s ob ta in ed w h ich in d ic a te s th a t th e compound has d if fe ren t m o lecu la r s t ru c tu re in v a r iou s s o lv e n t s . 51 The in fra red ab so rp t ion bands in Go(NN)^Clg a re s im ila r to the Cu(NN)g Brg spec trum in which b id en ta te coo rd ina tion o f the l ig and was s u g g e s te d . Three b and s a t 310(s), 285(m), and 257(m) a re ob se rv ed in th e Co(NN)gClg spec trum which cou ld be a s s ig n e d to th e c o b a l t - ch lo rine o r c o b a l t -n i t ro g en s t r e tc h in g f r e q u e n c i e s . In sk eep (51) h a s r e ­ ported th a t the m e ta l -n i t ro g en s t re tc h in g f requenc ie s for cobalt(II) c o pp e r ( I I ) , and zinc(II) complexes o f phen and b ipy o ccu r in the reg ion 300-264 cm \ bu t the in fra red sp e c t ra o f Co(NN)^(C10^)g • 4 HgO and Co(NN)gNOg)g com p lexes (Tables VII and XVIII) showed no bands in th is reg ion e x cep t modified l ig and b a n d s . This in d ic a te s th a t the bands ob se rv ed in the Co(NN)gClg a re c o b a l t - c h lo r in e s t re tch in g v ib ra t io n s . This is a l s o in ag reem en t w ith th e low conduc t iv i ty v a lu e of the com­ p lex which ag a in s u g g e s t s coo rd ina tion o f the ch lo rine a tom s . B an is te r e t a l . (52) have repo rted the p repa ra t ion and c h a r a c te r i ­ za t io n o f a compound Co [(CgH5)^PO Ig(NOg)2 and from th e m agnetic d a ta (4.69 B .M .) th ey a s s ig n e d a te t ra h ed ra l s tru c tu re for the complex . L a te r , th e m o lecu la r s t ru c tu re d e te rm ina tion o f the complex by X-ray s tu d ie s showed th a t the cobalt(II) w as surrounded by an ir regu la r a rrangem en t o f s ix oxygen a tom s , e a c h n i t r a te ion se rv ing a s a b id en ­ ta te l ig and (10). Although the m agne t ic d a ta and th e v i s ib le bands s u g g e s t a t e t r a ­ hed ra l geometry for the Co(NN)2Clg , the in frared spec trum in d ic a te s th a t th e n aph thy r id ine m o lecu le s a re coo rd in a ted th rough bo th n itrogens 52 to the cobalt(II) io n . The conduc t iv i ty v a lu e is in d ic a t iv e o f n o n - io n ic s p e c ie s and the in fra red d a ta support coo rd ina tion o f th e ch lo ride ions to the c o b a l t a tom . This means th a t th e c o b a l t atom is surrounded by four n i trogen s from two naph thy r id ine m o lecu le s and two ch lo rine a tom s . The complex is th e re fo re h e x a c o o rd in a te , bu t o c tah ed ra l geometry seem s u n l ik e ly in v iew o f the te t ra h ed ra l a p p ea ran ce o f the v i s ib le sp ec trum . Trigonal p r ism a t ic geometry is p o s s ib le in th is c a s e and can be co r re la ted w ith the v i s ib le spec trum in th e fo llow ing way . The two coo rd ina ting groups on n aph thy r id in e are much c lo s e r to g e th e r th an is u su a l in c h e la te m o le c u le s , and may be con s id e red in th is c a s e a s a " s l ig h t ly s p l i t" s in g le g roup . If two of the leg s o f a t r igonal p rism are fu sed in th is way an approx im ate te t rahed ron r e s u l t s . I t is th e re ­ fore s u g g e s te d th a t th is complex exh ib i ts tr igona l p r ism a t ic coo rd ina ­ t io n , t r e a t in g th e two n i trogen s in e a c h naph thy rid ine m o lecu le as s e p a ra te coo rd ina ting g ro up s , bu t th a t the proxim ity of th e two n i t ro ­ gens le a d s to a q u a s i - te t r a h e d ra l env ironment for the c o b a l t a tom , thu s a ccoun t ing for the v i s ib le sp ec trum . ' The u l t r a v io le t ab so rp t ion sp e c t ra o f ha l ide complexes ' in a b s o ­ lu te m ethano l so lu t io n s a re repo rted in Table XII. Comparison of the coo rd in a ted and free l ig and sp e c t ra showed th a t th e re w ere no s ig n i f i ­ c an t s h i f ts in th e p o s i t io n of the bands a lthough a few ex tra shou lders were ob se rv ed in Cu(NN)Clg and Cu(NN)Br2 s p e c t r a . These da ta were 53 ULTRAVIOLET ABSORPTION SPECTRA* Table XII X, nm v, kK emax ' M 1K Cu(NN)Cl2 308 32.5 6360 (303) (33.0) 6130 302 33.1 6610 296 33.8 6180 (290) (34.5) 5370 (284) (35.2) 4840 (264) (37.9) 6270 261 38.5 6340 (258) (38.8) 6240 Cu(NN)2C l2 309 32.4 12060 ' 301 33.2 12770 (297) (33.7) 11570 (290) (34.5) 9370 (285) (35.1) 7880 258 38.8 11070 Co(NN)2C l2 308 32.5 20550 301 33.2 .21600 (299) (33.4) 20490 (296) (33.8) 19140 (289) (34.6) 14640 (283) (35.3) 10890 258 38.8 15900 nm v ' kK W - m ^1 Cu(NN)Br2 308 32.5 7560 (304) (32.9) 7310 302 33.1 7750 (296) (33.8) 7930 (291) (34.4) 5590 (285) (35.1) 4260 (261) (38.3) 5590 257 38.9 5720 (251) (39.8) 5470 Cu(NN)2Br2 308 32.5 11550 (303) (33.0) 11200 301 33.2 12090 (296) (33.8) 10840 (290) (34.5) 8530 (284) (35.2) 6750 257 38.9 10130 CgHeNg 309 32.4 5700 (304) (32.9) 5280 301 33.2 5900 (297) (33.7) 5200 (290) (34.5) 4000 (283) (35.3) 2900 257 . 38.9 4310 54 Table XII (continued) X, nm v, kK Cu(dmNN)2C l2 6D13X' M 317 31.5 22250 309 32.4 18300 303 33.0 18100 (297) (33.7) 13100 (291) (34.4) 10400 (285) (35.1) 7700 254 39.4 9400 Cu(dmNN)2Br2 317 31.5 20600 309 32.4 17250 303 33.0 17000 (297) (33.7) 11900 (290) (34.5) 9100 (285) (35.1) 6350 (257) (38.9) 5000 (239) (41.8) 17000 315 31.7 9200 308 32.5 8760 304 32.9 8700 (297) (33.7) 6070 (291) (34.4) 4400 (285) (35.1) 3000 (272)" (36.8) 2600 253 39.5 3800 * P a re n th e se s r e p re s e n t shou lde rs ; ab so rp t io n s were m easu red in a b s o ­ lu te m ethano l s o lu t i o n s . 55 not u sed in any o f th e s t ru c tu ra l a n a ly s e s bu t are repo rted here for fu ture r e f e r e n c e . SUMMARY OF PART I: Two c om p le x e s , Cu(NN)Clg and Cu(NN)Brg , have been i s o la t e d . The d a ta a n a ly z ed in d ic a te th a t th e s e compounds have th e same s t r u c ­ tu r e , p robab ly a b in u c le a r 1,8-n aph thy r id in e -b r id g ed complex with a t l e a s t one and p robab ly bo th h a l id e s coo rd in a ted . The com p lexes Cu(dmNN)gClg and Cu(dmNN)gBrg have been s y n ­ th e s i z e d . The d a ta o b ta in ed in d ic a te coo rd ina tion o f th e naph thy rid ine m o le cu le s th rough one o f th e n itrogen a tom s . A te tra coo rd in a ted copper(II) ion (two n i trogen s and two h a l id e ions) w ith t ra n s geometry for th e s e complexes h a s been s u g g e s te d . The in fra red s p e c t r a of Cu(NN)gBrg and Cu(NN)gClg p rev iou s ly p repa red by Enwall were exam ined . The spec trum of the ch lo ride for w h ich the s t ru c tu re i s known was u s ed a s a re fe rence p o in t in compari­ son s of d a ta on the o th e r com pound s . The bromide a pp ea rs from the d a ta to con ta in c h e la te d n aph thy r id in e s and a d is to r te d o c tah ed ra l geometry . F in a l ly , th e Co(NN)2Clg complex w as p rep a red . The da ta s u g ­ g e s t a tr igona l p r ism a t ic geometry for th e complex w ith th e n aph thy r i- d in e s c h e la te d and ch lo r id e ions coo rd in a ted . Three coo rd ina tion ty p e s for 1 ,8 -naph thy rid ine and i t s d e r iv a t iv e s a re c le a r ly d is t in g u is h a b le in th is group o f compounds: m onoden ta te , a s in CutNlxOgClg and in th e dmNN comp lexes ; b id en ta te and ch e la ted to a s in g le m eta l atom a s in CuCNN^B^ and Co(NN)2C ^ ; and s y n - sy n b id e n ta te , b ridg ing two a d ja c e n t m eta l a tom s as in Cu(NN)C l2 and Cu(NN)Br2 . 56 57 PART II . PERCHLORATE COMPLEXES: S yn th e se s of p e rch lo ra te com p lexes from aqueous so lu t io n s r e s u l t e d , i n i s o la t io n o f th re e te t r a k is 1 ,8 -naph thy rid ine te t rahyd ra te compounds o f m anganese(II) , Cobalt(II), and n ick e l( I I ) . Two anhydrous te t r a k is com pounds , C u fN N ^ fC lO ^ g and Zn(NN)4( C lC ) ^ / were o b ­ t a in e d , and two compounds o f formula Zn(NN)^(ClO4)^ ' 4 H2O and Ag(NN)ClO4 . R e c ry s ta l l iz a t io n of the copper(II) complex from a mixture o f w a te r and a c e to n e gave a c ry s ta l l in e te t ra hyd ra te complex su i ta b le for X -ray d a ta c o l le c t io n . The a n a ly t ic a l and p h y s ic a l d a ta for p e rch lo ra te com p lexes a re g iven in Table III. The molar conduc t iv i ty m easu rem en ts o f th e com­ pounds in n i trom ethane or a b so lu te m ethano l so lu t io n s exh ib i t conduc ­ t iv i ty v a lu e s app rop r ia te for th r e e - io n s p e c ie s of the f i r s t row t r a n s i t io n m eta l complexes and a tw o - io n s p e c ie s for the s ilver(I) compound. The in fra red a b so rp t io n s p e c t r a o f th e complexes w ere reco rded in the reg ion 4000-250 cm \ The s e le c te d l ig and modes w h ich change upon coo rd ina tion a re l i s t e d in Table XIII. The sp e c tra o f a l l complexes , ap a r t from Ag(NN)ClO4 , a re id e n t ic a l and th e re were no s ig n i f ic a n t d if f e ren ce s from th e s p e c t ra o f th e anhydrous com pound s , e x cep t the lo s s o f the oxygen -hyd rogen s t re tc h in g band in the reg ion 3500- -13100 cm '. The sp e c t r a of th e hyd ra ted compounds did n o t con ta in any ab so rp t io n bands a t 700 cm ^ or 575 cm ^ (2 6,53) which c an be a s s ig n e d to coo rd in a ted w a te r v ib ra t io n f r e q u e n c i e s . This in d ic a te s th a t the Table XIII SELECTED INFRARED ABSORPTIONS (4000-250 CM 1J OF PERCHLORATE COMPLEXES * Band NN Mn(NN)4(C lO4)2 '4 H2O Co(NN)4 (ClO4) 2 '4 H2O Ni(NN)4 (ClO4) 2 " I 3500 v s , br 3100 v s , br 3300 v s , br II 1602 v s 1607 v s ' 1605 vs 1605 vs III 1555 vs 1575 s 1572 s 1565 s IV 1492 vs 1494 vs 1494 v s 1503 vs V 1228 s 1238 s 1237 s 1242 m VI -1085 v s , br 1085 v s , br 1090 v s , br VII 835 v s 835 vs 835 vs 835 s VIII 809 vs 803 vs 800 vs 805 vs IX 773 m ,s h 778 vs 782 vs 782 m X 760 vs 762 s 7sh 760 s 770 m XI 483 m ,s h « O a « • * 480 w XII 475 s 470 s 462 m 468 m XIII 402 s 405 m 405 m 420 m Table XIII (con tinued) Band Cu(NN) 4 (C104)2 - 4 H 20 Zn(NN)4(C lO4)2 Zn(NN)2(C lO4)2 *4 H2O Ag(NN)ClO I 3600 v s ,b r 3500 s ,b r . . . . II 1605 VS 1605 vs 1605 vs 1605 VS III 1565 S 1570 s 1565 s 1570 S IV 1492 S 1500 v s ,b r 1505 vs 1505 VS V 1240 m 1238 s 1238 s 1240 m VI 1090 v s ,b r 1110 v s ,b r 1095 v s ,b r 1085 VSyfc VII 838 VS 838 vs 842 vs 855 S VIII 805 VS 805 vs 837 s 835 VS IX 785 S • 780 vs 800 vs 802 VS X 760 m 760 s 780 v s 775 S XI 470 W 475 vw 475 m ,s h 490 VW XII 460 W ' 470 m 470 m 475 m XIII 415 W 405 m 425 m 420 m * The a s s ig nm en ts are: s> strong; vs , ve ry strong; m , medium; w, weak; vw, very weak; s h , shou lder; br, b ro a d . 60 w a te r m o lecu le s e x i s t a s l a t t i c e w a te r in th e c r y s t a l s . The s im ila r i ty ■ o f th e hyd ra ted and anhydrous sp e c t ra (Figure 10) in d ic a te s th a t the naph thy rid ine coo rd ina tion is ve ry s im ila r in the two s e r i e s . The lo s s of w a te r in the hyd ra ted compounds a t room tempera tu re in d ic a te s th a t the w a te r m o lecu les a re no t t ig h t ly bound in th e c r y s t a l s , and hence un coo rd in a ted , fu r ther supporting th e in fra red d a t a . The in fra red s p e c ­ tra o f th e s e compounds a re a l s o id e n t ic a l w ith the spec trum of anhydrous Cu(NN)^(C lO iJ)2 / wh ich is isomorph ic w ith Fe(NN)^(ClO iJ)2 (I) in w h ich the n ap h th y r id in e s a re c h e la te d to the iron atom (Figure 3). The s im ila r i ty o f the in fra red s p e c t r a , a s w ell a s the s im ila r i ty o f the v i s ib le s p e c t r a , s u g g e s t s th a t th e n aph thy r id in e s a re coo rd in a ted th rough bo th n i trogen s to the m eta l ion s in the en tire s e r i e s o f hydra ted and anhydrous p e rch lo ra te c om p le x e s . The s i lv e r complex is an e x c e p ­ t ion w h ich w ill be d i s c u s s e d in a s e p a ra te pa rag raph . The p e rch lo ra te ion in fra red bands in a l l p e rch lo ra te complexes a re s im ila r to the free ion bands and th e re is no in d ic a t io n th a t p e r ­ ch lo ra te ion is coo rd in a ted to the c en tr a l m e t a l s . The d i f f u s e - r e f le c ta n c e sp e c t ra o f cobalt(II) , n ickel(II) , and copper(Il) complexes a re l i s t e d in Table XIV. The p o s i t io n s of the b and s a re ve ry s im ila r to th o se r e p o r te d for o c tah ed ra l complexes (7,50, 54). The bands for th e anhydrous c om p lex e s , t e t r a hydra te c om p lex es , and m e ta l p e rch lo ra te h ex ahyd ra te s a re l i s t e d for com par ison . The d i f f u s e - r e f le c ta n c e s p e c t ra of the Cu(NN)^(ClOiJ)2 ' 4 H2O and 61 I.....i I L ( C IO jl)0 ,..MnO - - - - - H I . ... L uxW j ^ i F1V e - i - r - r : I ;..4 *:t—:j” Figure 10. Infrared Spec tra of C u (C gH gNg )^C lO j^ g ' 4 H^O and Cu(C8H6N 2)4(C lO4)2 . 62 Table XlV DIFFUSE REFLECTANCE SPECTRA OF PERCHLORATE COMPLEXES (CM-1 ) Compound Co(NN)4(C lO4)2 • 4 H2O Co(NN)4 (C lO4)2 Co(C lO^)2 ' GH2O Ni(NN)4 (OlO4)2 • 4 H2O N i(NN)4 (C lO4)2 N i(C lO 4)2 • GH2O Cu(NN)4(C lO4)2 • 4 H2O Cu(NN)4 (C lO4)2 Cu(C lO4)2 • GH2O Bands 28200 s h , 2 5300 s h , 21400, 20000 24400 w, 20600 s h , 18900, 16700 sh 25000 Sb, 21300 s h , 19700 26000 s h , 15500, 13800 sh 16300 25400, 21800 s h , 18900 s, 15400, 14000 16800 16700 13300 Table XV ELECTRONIC ABSORPTION SPECTRA OF PERCHLORATE COMPLEXES (CM -1) * In a c e to n i t r i l e so lu t ion Mn(NN)4 (C lO4)2 • 4 H2O Co(NN)4(C lO4) 2 • 4 H2O Ni(NN)4 (C lO4) 2 • 4 H2O Cu(NN)4 (C lO4)2 • 4 H2O In n itrom ethane so lu t ion Mn(NN)4(C lO4)2 * 4 H2O Co(NN)4(C lO4)2 • 4 H2O N i(NN)4(C lO4)2 • 4 H2O Cu(NN)4 (C lO4)2 • 4 H2O Bands 2500 sh(10), 24300 sh(7), 23800 sh(5) 25000 sh(35), 23700 sh(17), 19600 sh(145), 18500(210), 16700 sh(40) 26300 (45), 16150 (17) 27250 sh(35), 15750(80) 26000 (40), 23700 Sh(IO) 26800 (100), 19500 sh(250), 18500(350) 26000(60), 15850(14) . 26000 (300), 16100 (125) * P a re n th e se s r e p re s e n t molar a b s o r p t i v i t i e s . 63 Cu(NN)^(C IO^)2 in th e v i s ib le reg ion show s im ila r a b so rp t io n bands -I -Iwith maxima a t 16800 cm and 16700 cm r e s p e c t iv e ly . This aga in i n ­ d ic a te d th a t th e geometry o f the copper ion in both com p lexes is id e n t i ­ c a l w h ich is in good ag reem en t w ith th e in fra red ab so rp t ion d a ta . The v i s ib le ab so rp t io n b and s o f th e m eta l naph thy rid ine com p lexes appea r a t h ighe r f r equ en c ie s th an th o se of m e ta l p e rch lo ra te h ex ahyd ra te s wh ich in d ic a te s th a t n aph thy r id in e h a s a h igher l ig and f ie ld s treng th th an w a te r . This i s in ag reem en t w ith e a r l i e r work by H end ricker and Bodner (7), who have de te rm ined th e 10 Dq v a lu e s o f dmNN in the com­ p lex e s o f n ickel(II) , iron(II), and cobalt(II) w ith s to ich iom e try O - L M(dmNN) ,g and conc luded th a t dmNN h a s a l ig and f ie ld s t reng th s im i­ la r to p y r id in e . The so lu t io n sp e c t r a in a c e to n i t r i le and n itrom ethane of p e rch lo r ­ a te com p lexes o f t r a n s i t io n m e ta ls con ta in ing l e s s th an te n d e le c tro n s a re repo r ted in Table XVI. Comparison o f th e d i f f u s e - r e f le c ta n c e and so lu t io n sp e c t r a o f the complexes show s th a t the p o s i t io n s o f the bands change c o n s id e ra b ly , in d ic a t in g th a t th e l ig and s a re coo rd in a ted d if fe r ­ e n t ly in s o lu t io n . The mola r a b so rp t iv i ty o f the com p lexes a s w ell a s th e band p o s i t io n s change in bo th a c e to n i t r i le and n itrom ethane s o lu ­ t io n s w h ich is in d ic a t iv e o f th e v a r ia b le coo rd ina tion a b i l i ty of the s o lv e n t . B ecause of th e lo s s of w a te r o f hyd ra tion in hyd ra ted p e rch lo ra te c om p le x e s , a c c u ra te X -ray powder d a ta were ve ry d i f f ic u l t to c o l le c t 64 w ith the equ ipm en t a v a i l a b le . I t w as d ec id ed to ob ta in X -ray s ing le c ry s ta l d a ta by a s p e c ia l p rocedu re in o rde r to p ro te c t th e compounds from dehyd ra tion during the pe riod th a t th e compounds w ere expo sed to th e X -ray b e am . There fo re , X -ray s in g le c ry s ta l d a ta for hydra ted m an - ganese (II ) , cobalt(II) , n ickel(II) , and copper(II) com p lexes were ob ­ ta in e d by mounting the c ry s ta l in s id e a s e a le d g la s s c a p i l la ry c o n ta in ­ ing a sm all amount o f w a te r or mother l iquo r . The d a ta were c o l le c te d O by W e is s en b e rg m ethods u s ing CuKct (X= 1.54A) r a d ia t io n . Comparison o f th e film d a ta o f the compounds showed th a t on ly th e complexes of m anganese(II) and Cobalt(II) were isom o rph ic , in c o n t r a s t to da ta r e ­ ported in th e l i te ra tu re , in d ic a t in g th a t a l l anhydrous te t r a k is com­ pounds from m anganese(II) to copper(II) were isom orphous . The sp a c e group and c e l l p a ram e te rs were o b ta in ed to ve rify th is u nexpec ted s t ru c tu ra l v a r i a t i o n . C e ll d im ens ion s were de term ined by the methods g iven by Buerger (55) from ro ta t ion and W e is sen b e rg pho tog raph s . The film d a ta in d ic a te d th a t a l l complexes c ry s ta l l i z e d in m onoc lin ic c e l l s c e l l s e x c e p t the n icke l(I l) complex , w h ich c ry s ta l l i z e d in a t r ic l in ic c e l l . Cobalt(II) and Tnanganese(II) com p lexes were isom o rph ic , as no ted a b o v e . The c ry s ta l lo g rap h ic d a ta for a l l m onoc lin ic complexes a re l i s t e d i n Table XVI. The c ry s ta l d e n s i ty of th e copper(II) complex , Dm = 1.52 gem m easu red by f lo ta t io n , in d ic a ted th a t th e re are four m o le cu le s in th e un it c e l l . C le a r f ie ld e t a l . (3) have repo r ted two m o lecu le s p e r un it c e l l for the F e fN N ^ fC lO ^ g w h ich w as isomorphous 65 Table XVI CRYSTALLOGRAPHIC DATA OF PERCHLORATE COMPLEXES Compound Space Group 6 ang le a(A b(%) c(&) Cu(NN)4(C lO4)2 -4 H2O Ce ° r C2/ c ~ 8 8 ° .15.83 11.55 17.06 Mn(NN)4(C lO4)2 *4 H2O C2/m- C2 ° r Cm - 90° 15.85 12.90 8.45 Co(NN)4 (ClO4)2 '4 H2O C z /m 'C gO rCm - 9 0 ° 15.85 12.90 8.45 Zn(NN)4 (C lO4)2 ^ l / c ~ 8 9 ° 17.05 11.16 16.40 w ith th e co rre spond ing copper(II) compound. The Iron(II) complex c r y s ­ t a l l i z e d in a t r i c l in ic c e l l w ith s p a c e group P l . The work of Bodner and ■ H end ricke r (I) w ith anhydrous te t r a k is 1 ,8 -naph thy rid ine complexes in ­ d ic a ted th a t th e s t ru c tu re s o f a l l compounds from manganese(II) to copper(II) were i d e n t i c a l , and zinc(II) w as ve ry s im ila r . Our da ta c o n ­ firm the isomorph ism on Cu(NN)4 (C lO^)2 and Co(NN)4(C lO4)2 and in d ic a te th a t Zn(NN)4 (C lO4)2 does in d eed have a som ewha t d iffe ren t s t r u c tu r e . The zinc(II) complex c r y s t a l l i z e s in a m onoc lin ic c e l l w ith s p a c e group P2yc and p ang le of 89° which is in c o n t r a s t to the powder d a ta repo r ted e a r l i e r , a l though c ry s ta l l i z a t io n from aqueou s so lu tion may have in f lu en ced the c h a r a c te r o f th e c ry s ta l . The 8 ang le m easu red and c a lc u la te d from zero le v e l W e is s en b e rg pho tog raphs gave a va lue o f 8 8 -9 0 ° for a l l c om p lex e s . 66 Some a d d i t io n a l in formation abou t the geometry o f the ca t ion can be o b ta in ed from th e s e d a ta . The m u lt ip l ic i ty o f the g en e ra l p o s i t io n in C ^ /m or C2 / c is e ig h t- fo ld ; th a t o f th e g en e ra l p o s i t io n in C2 , C ^ , or Cm i s fo u r - fo ld . The d e n s i ty m easu rem en ts of Cu(NN)^(C10^)2 • 4 H2O in d ic a te s th a t the re a re four m o lecu le s p e r un it c e l l . S ince the s im i­ la r i ty in c e l l d im en s ion s to th e co b a l t and m anganese compounds s u g ­ g e s t s a c lo s e s t ru c tu ra l s im i la r i ty one can deduce th a t the number o f m o le cu le s p e r u n i t c e l l shou ld be two in t h e s e la t t e r c a s e s . If in t h e s e two compounds (c o b a l t and m anganese) the s p a c e group i s C2 / , the complex would th en be requ ired to have 2 /m symmetry . In v iew of th e d em ons tra ted s im ila r i ty o f th e i r in fra red sp e c t ra to th a t of Fe(NN )^(C lC^)2 , wh ich do e s no t even app roach 2 /m symmetry , th is s eem s u n l ik e ly . In Cm or C2 the complex would be requ ired to have 2 or m symmetry , bo th of w h ich a re app roached by the iron complex . S ince the same symmetry is requ ired o f the complex by the sp ace group in t h e s e two c om p le x e s , and s in c e th e s im ila r i ty in c e l l d im ensions s u g g e s t s a s im ila r s t ru c tu re to Cu(,NN)^(C10^)2 ' 4 H2O , i t seem s p rob ­ ab le th a t copper l i e s on s p e c ia l p o s i t io n s in th is compound , which would requ ire th a t C 2 , a c e n t r ic s p a c e group be the c o r re c t one . C en tr ic compounds a re e a s i e r to s tu dy than a c e n t r i c , and monoclin ic i s g en e ra l ly e a s i e r th an t r i c l in ic ; h en ce a s tru c tu re d e te rm ina tion on the copper compound s eem s l ik e ly to y ie ld b e t te r d a ta on th e coo rd ina tion geometry th an was o b ta in ed from the de te rm ined iron complex . 67 The anhydrous z in c complex ap p ea rs to have four m o lecu les p e r un it c e l l , from compar isons o f the c e l l d im en s io n s , and h ence one m o lecu le in a g en e ra l p o s i t io n . The compara tive e a s e o f de te rm ina tion in a m onoc lin ic s p a c e group compared to a t r i c l in ic one su g g e s ts th a t th is may a l s o be a good compound for s t ru c tu re s tu dy . Z n fN N ^ C lO ^ g ' 4 H2O : - The in fra red spec trum of Zn(NN)2(C lO^)2 • 4 H2O is s im ila r to th o s e o f the o th e r h y d ra te d te t r a k is c om p le x e s . There i s no in d ic a t io n th a t p e rch lo ra te an io n s or w a te r m o lecu le s a re coo rd in a ted to the z inc(Il) io n . The s im ila r i ty of the in fra red ab so rp tion bands s u g g e s t s th a t the n aph thy r id in e s are coo rd i­ n a ted th rough two n i trogen s to the c en tr a l m e ta l . This s u g g e s ts th a t zinc(II) ion i s su rrounded by four n i trogen a tom s . S ince te t ra h ed ra l geometry for four coo rd ina tion is u su a l for z in c ( I I ) , a te t ra h ed ra l a r rangem en t for th is complex is s u g g e s te d . Ag(NN )C lO^:- The spec trum of th e Ag(NN)ClO4 complex is d i f f e r ­ e n t from th o se o f th e te t r a k is and b is p e rch lo ra te c om p lex e s . The l ig and bands a re s im ila r to the spec trum of the Cu(NN)2C l2 in which n aph thy r id in e s a re coo rd in a ted th rough one of the n i t rog en s to the copper a tom . The p e rch lo ra te bands a re id e n t ic a l to th e free an ion bands w h ich in d ic a te s th a t the p e rch lo ra te ion is no t coo rd in a ted to th e s ilver(I) io n . However the d a ta o b ta in ed for th is complex is in su f f ic ie n t to s u g g e s t any p o s s ib le geometry for th e coo rd ina tion to th e s ilver(I) ion . 68 The u l t r a v io le t ab so rp t io n bands o f th e com p lexes in ab so lu te m ethano l so lu t io n s and th e i r molar a b so rp t iv i t ie s a re l i s t e d in Table XVII. Comparison of the free and coo rd in a ted l ig and band s shows no s ig n i f ic a n t sh i f ts in the p o s i t io n s o f any o f the b a n d s , a lthough a few ex tra shou ld e rs a p p ea r in the c om p lex e s . The free l ig and band a t 38900 cm * a p p ea rs a t a som ewhat low er f r equ en cy , 37700 cm- * in the s ilver(I) compound , bu t the s ig n i f ic a n c e o f th is s h if t i s u n c le a r a t p r e s e n t . SUMMARY OF PART I I . T e trak is p e rch lo ra te com p lexes o f m ang an e se ( I I ) , coba lt ( I I ) , n ic k e l ( I l ) , and copper(II) w ith 1 ,8 -naph thy rid ine o f the g en e ra l formula M (NN)^(C lOzI)2 ' 4 HgO have been p re p a red . From comparison o f the d a ta w ith th o s e of anhydrous te t r a k is compounds repo r ted in the l i t e r a ­ t u r e , c h e la t io n o f th e l ig and w as e s t a b l i s h e d in a l l c a s e s . All th e s e com p lexes c ry s ta l l i z e d in m onoc lin ic c e l l s ex cep t the n ickel(II) com­ pound w h ich is t r i c l in i c . Zinc(II) ion forms a b is c om p le x , . Z n (NN^ tC IO zI)2 ' 4 HgO . The s im ila r i ty o f th e l ig and c h e la t io n w ith the te t r a k is hyd ra ted compounds i s d i s c u s s e d . !Dodecahedral geometry for th e te t r a k is com p lexes and te t r a h ed ra l geometry for Zn(NN)g(ClCz|)g • 4 HgO has b een p ropo sed . 69 Table XVII ULTRAVIOLET ABSORPTION SPECTRA * X, nm v, KK sm av , M - 1 K X, nm v, kK e , M"max max Mn(NN)4 CS I OO 4 HgO Co(NN)4(C lO4) 2 • 4 H2O 307 32 .6 22700 308 32.5 ■ 22500 301 33.2 2 3 8 0 0 300 33.3 25100 ( 2 9 6 ) (33 .8 ) 20900 (295) (33.9) 20900 (290) (34.5) 17100 (290) ( 34 .5 ) 16400 ( 2 8 3 ) (35 .3 ) 1 1 7 0 0 ( 2 8 3 ) (35 .5 ) 11800 ( 2 7 2 ) (36 .8 ) 1 2 3 0 0 ( 2 7 6 ) (36 .2 ) 1 0 9 0 0 (269 ) (37.2) 1 3 7 0 0 (271) ( 36 .9 ) 13000 ( 2 6 4 ) .(37.9) 15700 ( 2 6 3 ) (38.0) 1 6 1 0 0 257 38.9 1 7 4 0 0 2 58 38 .7 17300 Ni(NN) 42 ' 4 H g O Cu(NN) 4 2 ' ^ H g O 3 0 9 32 .4 1 0 6 0 0 309 32 .4 1 1 4 5 0 ( 3 0 3 ) ( 3 3 . 0 ) 1 0 6 0 0 ( 3 0 3 ) (33 .0 ) 1 0 9 3 0 3 0 1 33.2 1 1 2 0 0 3 0 1 33.2 1 2 0 3 0 ( 2 9 6 ) (33 .8 ) 9 9 1 0 ( 2 9 6 ) (33 .8 ) 1 0 5 0 0 ( 2 9 0 ) ( 3 4 . 5 ) 7 6 6 0 ( 2 9 0 ) (34 .5 ) 8 1 5 0 ( 2 8 3 ) (35.3 ) 5 3 0 0 ( 2 8 4 ) (35 .2 ) 5 8 5 0 2 5 7 38.9 8 1 0 0 2 5 8 38 .8 1 0 2 0 0 C o ( N N ) 2 ( N O 3 ) 2 C o ( N N ) O CO * 6 H 2 O 3 0 9 3 2 . 4 6 4 0 0 3 0 9 3 2 . 4 1 5 1 0 0 ( 3 04 ) (32 .9 ) 6 1 5 0 ( 3 0 4 ) (32 .9 ) 1 4 5 0 0 3 0 2 33.1 6 8 0 0 3 0 1 33.2 1 5 8 5 0 ( 2 9 6 ) (33 .8 ) 5 9 5 0 ( 296 ) (33 .8 ) 1 3 8 5 0 ( 2 90 ) ( 3 4 . 5 ) 4 5 0 0 ' ( 2 90 ) ( 3 4 . 5 ) 1 0 8 0 0 ( 2 8 4 ) ( 3 5 . 2 ) 3 4 0 0 ( 2 8 4 ) ( 3 5 . 2 ) 1 0 1 5 0 2 5 8 38.8 4 8 0 0 2 5 9 38 .6 1 1 1 5 0 85 Table XXII (con tinued) X, nm V, kK w T W b y X, nm v, kK e , M 1max Cu(NN)216 (NO3)2 Cu(NN)2(NC)3h 309 32.4 13050 309 32.4 11300 301 33.2 13650 301 33.2 11900 (297) (33.7) 12 300 (297) (33.7) 10800 (290) (34.5) 9600 (290) (34.5) 8650 (284) (35.2) 7500 (284) (35.2) 6750 (274) (36.5) 7600 (274) (36.5) 6750 (268). (37.3) 9250 . (268) (37.3) 8100 (264) (37.9) 10300 (264) (37.9) 9050 259 38.6 10600 254 39.4 10400 Zn(NN) ^(NOg) 2 ' 6 H2 ° Ag(NN)NO3 309 32.4 24000 309 32.4 6200 301 33.2 25150 301 33.2 6450 (297) ■ (33.7) 22100 (297) (33.7) 5800 (290) (34.5) 15900 (290) (34.5) 4400 (284) (35.2) 11900 (285) (35.1) 3620 (273) (3 6.6) 11700 (277) (36.1) 3400 (271) (36.9) 13150 (273) (36.6) 3900 259 38.6 17650 260 38.5 5050 * P a re n th e se s r e p re s e n t s h o u ld e r s . 86 The compound Cu(NN)2 ^g(NO3)2 w as p repa red from aqueous s o lu ­ t ion and the d a ta in d ic a te th a t the n aph thy r id in e s a re c h e la te d to the coppe r a tom . No c e r ta in a s s ig nm en t o f s t ru c tu re can be made in th is c a s e . The complex N i(NN)2(NO3)3 ’ 4 H2O h a s been s y n th e s iz e d . The d a ta s u g g e s t c h e la t io n o f the l ig and s w ith w a te r m o lecu le s coo rd in a ted . O c tah ed ra l or d od ecah ed ra l geometry for the n ickel(II) ion a re p o s s ib le e x p lan a t io n s o f the d a ta . Experiments w ith s ilver(I) ion re s u l te d in i s o la t io n o f an Ag(NN)NO3 complex in which the n aph thy r id in e is coo rd in a ted mono- d e n ta te ly to th e s i lv e r a tom . The geometry o f the coo rd in a tion complex is no t known. 87 PART IV. COPPER(I) COMPLEXES In 19 70 s e v e ra l t r i s com p lexes o f 2/7 -d im e th y l - l /8 -naph thy r id in e w ith v a r iou s m e ta ls o f g en e ra l formula M (dm NN ^C lO ^g , in c lud ing a brown copper(II) com pound , were repo r ted (7). The a n a ly s i s p re sen ted in th a t repo rt in d ic a te d th a t a l l complexes con ta in ed o c tah ed ra l ly c o ­ o rd in a ted b id en ta te n a p h th y r id in e . Copper(II) compounds in which the m e ta l atom is su rrounded by s ix n i trogen a toms are no rm a lly b lu e , and the repo r t o f a brown copper(II) complex so coo rd ina ted w as thus ra th e r u n u su a l . A ttempts to d u p l ic a te the s y n th e s i s o f th is brown mate r ia l w ith ' bo th NN and dmNN were m ad e . The d e s i red compounds were ob ­ ta in ed bu t c anno t be c h a ra c te r iz e d a s copper(II) c om pound s . The two p roduc ts were an a ly z ed and c h a r a c te r iz e d . M agne tic moments and e le c t ro n ic sp e c t ra in d ic a te d th a t bo th compounds were copper(I) com­ p le x e s . M oreover , for com par ison , copper(I) ch lo ride complexes of n aph thy r id in e s were p repa red d i re c t ly from copper(I) ch lo r id e and n a p h th y r id in e s . Four copper(I) com p lexes o f 1 ,8 -naph thyrid ine and i t s 2,7-dimethyl d e r iv a t iv e con ta in ing ch lo r ide and p e rch lo ra te an ions have been sy n ­ th e s i z e d and c h a r a c e r iz e d in th is r e s e a r c h . The a n a ly t ic a l and p h y s ic a l d a ta a re g iven in Table V. C onduc t iv i ty m easu rem en ts on the copper(I) n aph thy r id in e com p lexes in a c e to n i t r i l e , n i t rom e th an e , or ab so lu te m ethano l in d ic a te th a t the complexes in so lu tion a re ion ic ; the va lue 88 ob ta in ed co rre spond s to s in g ly ion iz ing s a l t s , wh ich a g re e s w ith r e ­ s u l t s repo r ted e a r l ie r for copper(l) com p lexes (6). M agne t ic s u s c e p t ib i l i ty m easu rem en ts bn the com p lexes by the Gouy method in d ic a te th a t the complexes a re d iam agne t ic . V isib le and u l t r a v io le t sp e c t ra show on ly charge t r a n s fe r bands a s s o c i a b l e w ith the l ig a n d . These two o b se rv a t io n s c le a r ly e s t a b l i s h the formal ox ida tion s ta t e o f th e m eta l in t h e s e complexes a s +1 . The complex CUg(NN)Clg gave a rep roduc ib le m elting po in t a t 292 ± .1°C . All o th e r compounds in th is group decomposed w ithou t m elting a t tem pe ra tu res a t or be low 2 7 0 °C . The in fra red s p e c t ra of the copper(I) compounds a re summarized in Table XXIII. A ss ignm en ts for the l ig and bands ' a re g iven in the l i te r a tu re (37). Cu(NN) ClO^: — The in fra red spec trum of th is complex was com­ pa red w ith th o s e o f com p lexes d i s c u s s e d e a r l ie r in th is t h e s i s . The l ig and b and s are s im ila r to Cu(NN)Clg and Cu(NN)Brg s p e c t r a in which n aph thy r id in e s a re b e l ie v ed to b ridge a c ro s s two copper(ll) io n s . This s u g g e s t s a s im ila r s t ru c tu re for the copper(I) compound. The b ro ad , - I -Ivery s trong p e rch lo ra te bands a t 1115 cm - and 1087 cm (an tisymmetr ic s t re tch ) and the band s a t 635(m) cm ^ and 622(s) cm * (an tisymmetr ic bend) a re c h a r a c te r i s t i c of coo rd in a ted p e rch lo ra te (26) , When p e r­ ch lo ra te ion c o o rd in a te s i t s symmetry i s low ered from T ^ (free ion) to Cg (coo rd ina tion th rough one oxygen) or Cgv (coo rd ina tion through two Table XXIII * SELECTED INFRARED ABSORPTIONS (4000-250 CM X) OF COPPER(I) COMPLEXES Band NN Cu(NN)ClO4 Cu2(NN)Cl2 Band dmNN Cu(dmNN)2C104 Cu2(dmNN) CD I 1555 v s 1563 m 1565 s I ' 1532 s 1555 m 1540 w II 1492 vs 1507 vs 1502 vs II 1505 vs 1517 vs 1517 vs III 1465 s 1486 vs 1460 w III 1360 w 1372 s 1375 m IV 1395 s 1402 m 1388 m IV 1240 m 1252 vw 1253 vw V 1228 s 1238 v s ■ 12 66 vw V 1206 w 1218 m 1211 w VI • O • • 1148 v s ,b r • • • • VI • • • • 1087 v s ,b r VII 1128 v s • • • • 1135 w VII 847 vs ' 855 vs 866 v s VIII • • • • 1115 v s ,b r « » « O VIII 805 vs 810 w 812 m IX • • • • 1087 v s ,b r ■ 0 • • IX 778 vs 798 vs 788 vs X 1027 s 1040 s ,b r 1042 m X • • a 775 w 776 m XI 835 v s 853 m 835 vs XI 622 m 648 w 650 vw XII 808 vs 840 s 795 vw XII . , # 618 s XIII • 773 m, sh 825 w 790 s , s h XIII 442 m 457 w 450 vw XIV • • • 797 v s , sh • • • XIV 343 m 350 w 348 vw XV 758 vs 792 vs 770 w, sh XVI 600 w 637 w XVII 635 m « • • XVIII 622 s XIX 537 m 542 w 538 vw * The a s s ig nm en ts are: s, s trong ; v s , ve ry s trong; m, medium; w, weak; vw, very weak; s h , shou lder; br, b ro a d . 90 U 15 18 20 I i - T r i r 25 30 WO ^ C u ( C m H m N0 )0 C I O , -I-— ■■?— i Figure 12. Infrared Spec tra of C u ( ^ClO^ and Cu (CgH6N2)ClO4 . 91 o x y g e n s ) . Each o f the two in fra red a c t iv e bands is s p l i t in to two com­ ponen ts in Cgv symmetry and in to th ree components in symmetry (8,2 6 ,60). The free p e rch lo ra te bands a t abou t 1100 cm * and 620 cm ^ s p l i t in to two bands r e su l t in g in four bands a s ob se rv ed in th is com­ pound (Figure 12). T hese bands in d ic a te th a t the p e rch lo ra te ion is c o ­ o rd in a ted th rough one o f the oxygen a tom s to the copper atom (s e e Figure 12). The Cu(NN)ClO^ is p robab ly a p o ly nuc le a r complex with n aph thy r id in e m o lecu le s b ridged a c ro s s two copper a tom s and p e rch lo r­ a te s coo rd in a ted th rough one o f the oxygens to the copper(l) io n s . The b in u c le a r s t ru c tu re shown in Figure 13 i s su g g e s te d for th i s complex . A ve ry s im ila r copper(l) complex o f d iazoam inobenzene h a s b een p rev i­ o u s ly repo r ted (31). OClOg Figure 13. S ugges ted s t ru c tu re for Cu(NN)ClO^ complex . CufdmNNjgClOg and CugWmNNjClg:— The in fra red sp e c tra of copper(l) complexes w ith 2 ,7 -d im e th y l- l ,8 -n ap h th y r id in e a re l i s te d in Table XXIII. The sh if ts o f the l ig and band s upon coo rd ina tion are 92 s im ila r in both Cu(CimNN)2ClC^ and Cu2 (^mNN)G l2 com pounds . The s p l i t t in g o f the free l ig and band a t 1128 cm * is no t o b se rv ed in the spec trum o f the Cu2 (dmNN)C l2 . This reg ion of the spec trum in Cu(dmNN)2C10g is cove red by p e rch lo ra te ion bands and th e l igand bands a re no t o b s e rv a b le . Three v e ry s trong bands w h ich o ccu r a t 847, - I 805, and 778 cm in the free l ig and spec trum a re o b se rv ed a s two very s trong and two medium and weak bands a f te r coo rd in a t io n . The p e r ­ ch lo ra te an ion bands in Cu(dmNN)2C10^ o c cu r a s a broad band a t 1087(vs) cm "*■ and a sharp s ing le band a t 618(s) cm \ in d ic a t iv e of io n ic p e rch lo ra te (7,54) (Figure 12). The l ig and bands in copper(l) com­ p le x e s of dmNN are s im ila r to th o se o f Cu(dmNN)2X2 (X= Cl or Br) in wh ich m onoden ta te coo rd in a tion to th e copper a toms w as s u g g e s t e d . The c o pp e r -ch lo r in e s t re tc h in g frequency, w as no t o b se rv ed in the s p e c ­ trum o f Cu2(dmNN)Cl2 . The u l t r a v io le t ab so rp t io n bands o f Cu(dmNN)2C10^ are s im ila r in sh ape to th o se o f dmNN comp lexes o f copper(II) io n , bu t d iffe ren t from th e o th e r copper(I) com p lexes in th is s tu d y . There i s g en e ra l ly a sharp in c r e a s e in in te n s i ty of th e u l t r a v io le t spec trum of th e copper(I) com­ pounds , bu t in th is compound no su ch in c r e a s e is o b s e rv e d . This s im i­ la r i ty o f the u l t r a v io le t ab so rp t ion to th a t o f m ononuc lear copper(II) compounds and the d i f f e ren ce s from o th e r copper(l) compounds su g g e s ts a ve ry d if fe ren t s t ru c tu re for th is complex . 93 In the Cu(dmNN)2C104 complex th e n aph thy r id in e s a re coordinated th rough one of the n i t rog en s and th e p e rch lo ra te an ion e x i s t s a s an io n ic s p e c i e s . The s to ich iom e try o f Cu(dmNN)2C10^ complex is id e n t i ­ c a l to th e Cu(Mpy)2ClO4 and Cu(Phen)2ClO4 compounds (6), but coo rd i­ na tion m us t be v e ry d if fe ren t in the dmNN complex i f the l ig and is monoden ta te a s in d ic a te d in th e in fra red sp ec trum . Thus th e da ta a v a i l ­ ab le a re in su f f ic ie n t to de te rm ine the coo rd in a te geometry o f the copper in Cu(dmNN)2C104 . The e a r l i e r workers (7) have a s s ig n e d a b id en ta te coo rd ina tion for th i s same com p lex , e r ron eou s ly repo rted a s Cu(dmNN)g(C lO^)2 ; however the p o s i t io n s and in te n s i t i e s of the bands in the reg ion 9 0 0 -7 0 0Cm * do no t co rre spond to the b and s l i s t e d for the r e s t o f th e tr i s c om pound s . This work s u g g e s t s th a t dmNN is coo rd i­ n a ted m onoden ta te ly and th e p e rch lo ra te i s io n ic , bu t i s n o t su f f ic ien t to in d ic a te a coo rd in a te geometry for the copper(l) ion . Comparison o f the in fra red spec trum of Cu2(dmNN)Cl2 w ith th o se o f Cu(dmNN)2C l2 and Cu(dmNN)2Br2 in w h ich monoden ta te n aph thy r i- d ine coo rd ina tion i s h y po th e s iz ed shows th a t the sp e c t ra a re very s im i la r . This s u g g e s t s th a t the dmNN lig and in th is compound is a l s o m onod en ta te . Cu2 (NN)Cl2: - The in fra red spec trum of the Cu2 (NN)C l2 is s im i­ la r to th a t of Cu(NN)2C l2 in which n aph thy r id in e s are coo rd in a ted th rough one of the n i t rog en s to the copper a tom . The s in g le band a t 113 6(s) cm ^ in th e copper(Il) complex app ea rs a t 1135(w) cm ^ in the 94 copper(I) com pound . The v e ry s trong 835 cm * free l ig and band occu rs w ithou t any s h i f t a s a s in g le sharp band and the l ig and band a t 760 cm —i appea rs a s a weak shou ld e r a t 770 cm a f te r c om p lex a t io n . This in d i ­ c a te s th a t n aph thy r id in e i s coo rd in a ted th rough one o f th e n itrogens to th e copper(I) ion a s o c cu rs in th e C uCNN ^C ^ complex . No bands a re o b se rv ed in the reg ion 350 -250 cm * which can be a s s ig n e d to the c o pp e r -ch lo r in e s t r e tc h in g f requency . The c o pp e r -ch lo r in e s t re tch ing f requency o f Cu21(CHgN=NCHg)Cl9 ha s b een repo rted a s a weak band a t 311 cm * (28). The w e ak n e s s o f th is band may a ccoun t for the fa ilu re to find i t in th e spec trum o f CUg(NN)Cl^. The sharp m e lting po in t o f the complex a t 292 ± 1°C s u g g e s t s th a t th e complex is m o le cu la r and hence th a t the ch lo r ine a tom s a re coo rd in a ted to the copper(l) io n . M o lecu la r w e igh t d e te rm in a t ion s would be ve ry v a lu ab le but the low so lu b i l i ty of th e compounds did no t pe rm it m o lecu la r w e igh t m e a su rem en ts . The u l t r a v io le t s p e c t ra o f a l l th e c om p le x e s , a p a r t from the CutdmNNlgClO^, w ere s im ila r in s h a p e , bu t d iffered from tho se qf copper(II) compounds d i s c u s s e d e a r l i e r . There w as a sh a rp in c re a s e in in te n s i ty o f the spec trum w ith s ev e ra l shou lde rs above 36000 cm . The band a t abou t 38000 cm * p re s e n t in copper(II) com p lexes (Table VII) does n o t a p p ea r in the CUg(NN)Clg, CUg(dmNN)Clg, and Cu(NN)ClO^ comp lexes (Table XXIV), bu t s in c e no a s s ig nm en t o f th is band has been made the s ig n i f ic a n c e o f th is a b s e n c e i s u n c le a r . _1 95 Table XXIV ULTRAVIOLET ABSORPTION SPECTRA* X,nm v, kK w T t b y X, nm v - kK em ax ' M~ Cu(NN)ClO4 Cu2(NN)C l2 307 32 .6 5650 308 32.5 5750 300 33.3 6000 (302) (33.1) 5750 (295) (33.9) 5300 .301 33.2 6100 (289) (34.6) 4100 ( 2 9 5 ) (33 .9 ) 5500 (283) (35 .3 ) 3100 ( 2 8 8 ) (34 .7 ) 4200 (284) (35.2) 3300 Cu(dmNN) ,C lO 4 Cu2MmNN) CI2 315 31.8 19480 315 31.8 10500 307 32 .6 17300 307 32 .6 9000 302 33.1 17000 302 33.1 8800 (297) (33.7) 12800 ( 2 9 6 ) (33 .8 ) 6100 (290) (34.5) 10200 (290) (34.5) 4700 (285) (35.1) 8600 (283) (35.3) 3200 250 40.0 11500 * P a re n th e s e s r e p re s e n t s h o u ld e r s . 96 The s im ila r s to ich iom e try o f Cu^(NN)Clg and Cug(dmNN)Clg s u g ­ g e s t s some re la t io n b e tw een th e s e s t r u c tu r e s . D iazene complexes w ith the g en e ra l formula (RN=NR)CUgClg have been s tud ied p rev io u s ly (28). An X -ray c ry s ta l lo g rap h ic s tu dy o f a r e p re se n ta t iv e com pound , (CHgN=NCHg)CUgClg h a s shown (30) th a t the complex c o n s i s t s of in ­ f in i te ch a in s of copper and ch lo r ine a tom s (Figure 14). However the m elting po in t o f the C u7(NN)Clg s u g g e s t s th a t i t i s m o lecu la r and h ence an in f in i te M -C l-M bridged l a t t i c e seem s u n l ik e ly . Moreover a s t ru c tu re s im ila r to th e d ia z in e s is no t p o s s ib le for n aph thy r id in e c om pound s . N aph thy rid ine is a f la t rig id m o lecu le and coo rd ina tion to two a d ja c e n t c h a in s o f CuCl w ith n aph thy r id in e s ly ing in be tw een the c h a in s requ ire s the s t e r i c a l ly im po ss ib le ro ta tion of one o f th e n i trogen a tom s 180° around the C=C of the r ing . The in frared s p e c t ra o f the compounds do no t in d ic a te any bridging p rope r t ie s for l i g a n d s . - C u — — Cu ---- -CH Figure 14. S tructu re o f (CHgN=NCHg)CugClg compound. 97 A s tru c tu re ra th e r d if fe ren t from th a t o f the d ia z en e i s requ ired , bu t th e re is no c le a r in d ic a t io n in th e d a ta a s to the n a tu re o f th is s t r u c tu r e . This problem c le a r ly m erits fu r ther s tudy . SUMMARY OF PART IV. Two copper(I) complexes o f 1 ,8 -n aph thy r id in e , Cu(NN)ClO^ and C ug(NN )C lg , have b een s y n th e s iz e d . From compar isons o f the da ta w ith th o se complexes d i s c u s s e d ea r l ie r , a b ridged n aph thy r id ine coo rd i­ n a t io n a c ro s s the two copper(l) ions in Cu(NN)ClO^ w ith p e rch lo ra te ion be ing coo rd ina ted m onoden ta te ly to th e copper atom w as found. In CUg(NN)Clg com p lex , m onoden ta ted coo rd ina tion of th e l ig and was s u g ­ g e s te d and a p o s s ib le s t ru c tu ra l geometry w as d i s c u s s e d . S im ila r ly , two copper(I) complexes o f 2 ,7 -d im e thy l-1 ,8 - n aph thy r id ine , Cu(dmNN)gC104 and Cug(dmNN)Clg were i s o la t e d . M onoden ta te coo rd in a tion for the l ig an d s w as a s s ig n e d , a mononuclear s p e c ie s for Cu(dmNN)gClC^ and p o ly nu c le a r a rrangem en ts for CUg(dmNN)Clg a re s u g g e s te d . A P P E N D IX 99 SULFATE AND ACETATE COMPLEXES Severa l su l fa te and a c e ta t e compounds of t r a n s i t io n meta l ions w ith 1 ,8 -naph thy rid ine have been s y n th e s iz e d . The d a ta on th e s e com­ p le x e s have no t b een a n a ly z e d , bu t th e a n a ly t ic a l and p h y s ic a l d a ta a re g iven in Tab les XXV and XXVI r e s p e c t iv e ly . SULFATE COMPLEXES: Cu(NN)SO4 - 4 FI2O and Cu(NN)SO4 *2 H2O : - To a so lu t io n of 0.125 g (0.5 mmol) o f CuSO4 * 5 H2O in 10 ml o f w a te r 0.09 I g (0.7 mmol) o f NN was added in a Petri d i s h . This b lue so lu tion w as k ep t in a c lo sed chamber con ta in ing a c e t o n e . Upon d iffu s ing a ce to n e in to the so lu tion for 24 hours th ree d if fe ren t k inds o f c ry s ta l s were o b ta in ed . Two forms which were g reen and b lu i s h -g re e n w ere a i r s t a b l e . They were c o l l e c t ­ ed m anua l ly on a f i l te r p ape r and were a i r d r i e d . The a n a ly s e s of th e s e two forms w h ich w ere s e p a ra te d m anua l ly showed th a t th ey had the same s to ich iom e try . The th ird form , tu rquo ise b l u e , w as no t a ir s ta b le and formed a l ig h t b lue powder a t room tem p e ra tu re . These la th -fo rm u n s ta b le c ry s ta l s were s e p a ra te d on a f i l te r p ape r and w ere ana ly zed imm ed ia te ly , before decom pos it ion Could take p la c e . The a n a ly s is showed th a t th is u n s tab le compound con ta in ed four m o lecu le s of h yd ra ­ t ion w a te r , but the powder ob ta in ed a f te r lo s s of w a te r c on ta in ed only two m o lecu le s o f w a te r . The w e igh t lo s s in the compound , which was 100 de term ined by w eigh ing the c ry s ta l s be fo re and a f te r d e com po s i t io n , w as c o n s i s t e n t w ith th e s e d e te rm in a t io n s . Cu(NN)2SO4 : - To a so lu t ion o f 0.2 5 g (Immol) o f CuSO4 ' 5 H2O in 40 ml o f d imethylformam ide w as added 3-5 drops o f c o n cen tra ted H2SO4 fo llowed by add it ion o f 0.26 g (2 mmol) o f NN . The so lu t io n was re ­ f luxed for s e v e ra l m in u te s . This so lu t io n w as f i l te red from the p re c ip i ­ t a t e , i f a n y , and th e volume o f the f i l t r a te w as reduced to abou t 20 ml by k eep ing the so lu t io n warm and under reduced p r e s s u r e . The c o n cen ­ t ra te d so lu t io n w as k ep t a t room tem pe ra tu re un til c ry s ta l l i z a t io n was com p le ted . The tu rq u o is e -b lu e p re c ip i ta te w as f i l te red and r e c ry s ta l ­ l iz e d from d im ethy lfo rmam ide. The c ry s ta l s were w a sh ed w ith chloroform fo llowed by a c e to n e and d ried over ca lc ium c h lo r id e . Co(NN)SO4 1S H2O , Ni(NN)SO4 - 4 H2O , and Zn(NN)SO4 • 4 H2O: - A so lu t io n o f 0.2 81 g ( I mmol) of CoSO4 '7 H2O , or 0.2 63 g (I mmol) of NiSO4 • 6 H2O , a n d /o r 0.2 87 g ( I mmol) o f ZnSO4 1 7 H2O in 10 ml of w a ter c on ta in ing 0.13 g ( I mmol) o f NN w as d iffu sed by a c e to n e for 2 4 h o u r s . The n eed le - fo rm c ry s ta l s o f g r e e n ish -b lu e n ic k e l , p ink c o b a l t , and wh ite z in c complexes were i s o l a t e d . The c ry s ta ls were c o l le c te d by f i l t r a t io n , w ashed w ith ch lo ro fo rm , and a ir d r ied . These compounds were r e c ry s t a l l i z e d from th e i r aqueous so lu t io n s by a s im ila r method. Mn(NN)SO4 1 5 H2O : - A so lu t io n o f 0.169 g (Immol) o f MnSO4 ’ H2O and 0.2 g (1.54 mmol) o f NN in 15 ml of w a te r w as kep t in an i c e - b a th for a few hours un ti l a w h ite p re c ip i ta te w as o b ta in ed . This 101 p re c ip i ta te w as c o l le c te d by f i l t ra t io n and was r e c ry s ta l l i z e d from i t s aqueou s so lu tion by the same p ro c e d u re . The white n e e d le s were c o l­ le c te d on a f i l te r p a p e r , w a sh ed w ith ch lo ro fo rm , and a i r d r ied . Cu(NN)SO^ ° H gO ' CHgOH: — To a so lu tion of 0.2 5 g (Immol) of CuSQg * 5 HgO in 10 ml o f w a te r 0.13 g ( I mmol) o f NN w as added followed by add it ion of 30 ml o f a b so lu te m ethano l o r m ethano l-ch lo ro fo rm m ix­ tu re (3 ;1 ) . Upon s tand ing for 30 m inu tes th e b lue c ry s ta l s were c o l l e c t ­ ed in a s in te re d g l a s s fu nn e l , w a sh ed w ith ab so lu te m e th ano l , and a ir d r i e d . Ag2(NN)gSO4: - To a so lu t ion o f 0.155 g (0.5 mmol) o f Ag2SO4 in 70 ml o f hot w a te r 0.13 g (I mmol) o f NN in 10 ml o f warm w a te r was a dd ed . The so lu t io n w as coo led s low ly un t i l c ry s ta l l i z a t io n was com­ p le te d . The wh ite n eed le - fo rm c ry s ta l s were c o l le c te d by f i l t ra t io n , w a sh ed w ith w a te r fo llowed by a c e to n e , and dried over ca lc ium ch lo r­ id e . The r e c ry s ta l l i z a t io n of the compound w as performed from hot w a te r . ACETATE COMPLEXES: Ni(NN)2(OAc)2 * 4 H g O : - A so lu t io n of 0.245 g (Immol) of n icke l(I l) a c e ta t e te t ra hyd ra te in 10 ml o f w a te r con ta in ing 0.2 6 g (2 mmol) of NN w as k ep t a t room tempera tu re to d e c r e a s e the vo lume o f the s o lu ­ t ion to a minimum by s low ev apo ra t io n . The c le a r g reen so lu tion was kep t in a chamber con ta in ing e i th e r a c e to n e or a c e to n e - e th y la c e ta te 102 m ix tu re . After d if fu s ion for 24-72 h o u r s , g reen w e l l- fo rm ed c ry s ta ls were c o l le c te d m anua l ly , w a sh ed w ith ch loroform , and d ried over ca lc ium ch lo r id e . The complex w as r e c ry s ta l l i z e d by the same pro­ c edu re . Co tNN^fOAcjg * 4 H g O : - An aqueous so lu tion o f 0.249 g (Immol) o f Co(OAc)g ' 4 HgO and 0.2 6 g (2 mmol) o f NN in 10 ml o f w a te r w as p re ­ p a re d . Dark pink c ry s ta l s were o b ta in ed by s low evapo ra t io n of the so lu t io n a t room tem p e ra tu re . The w e ll- fo rm ed c ry s ta ls were co l le c te d m anua l ly on f i l te r p ap e r and a i r d r ied . These c ry s ta ls w ere purif ied by r e c ry s ta l l i z a t io n from aqueou s s o lu t io n . OLEXXFSE,he F2sW iA a so lu t io n of 0.4 g (2 mmol) of Cu(OAc)2 • HgO in 30 ml o f warm DMF 0.52 g (4 mmol) of NN w as added . This s o lu t io n w as k ep t in a d e s ic c a to r con ta in ing con cen tra te d HgSO^ under reduced p re s su re for a few d a y s . The tu rq u o i s e -b lu e c ry s ta ls were f i l te red in a s in te re d g la s s fu nn e l , w a sh ed w ith a b so lu te e th a n o l , and d ried over ca lc ium ch lo r id e . Cu(NN)(OAc)2 '2 HgO: — An aqueou s so lu tion o f 0.199 g (Immol) o f Cu(OAc)2 * HgO and 0.13 g (Immol) o f NN in 10 ml o f w a te r in a sm all Pe tr i d is h w as k ep t p a r t ia l ly covered a t room tem pe ra tu re . The blue c ry s ta l s were f i l t e r e d , w a sh ed w ith 95% e th an o l , and a i r d r ied . Table XV SULFATE COMPLEXES t % C a l c d . - t ” - ' • % Found Color Conduct. A (molar) C H Ma AD C H M A 2 .cm mho Cu(NN)SO4 M H 2O 17.56 26.55 17.64 17.64 26.32 Turquoise “ ' ' Cu(NN)SO4 M H2O 29.54 3.09 19.50 29.49 29.81 2.87 19.42 29.35 Blue-^green 6 Cu(NN)2SO4 45.79 2.88 15.13 22.88 44.88 3.01 14.96 22.94 Turquoise 7 Cu(NN)2SO4 • H2O * CH3OH 43.44 3.86 13.52 20.44 43.52 3.75 13.5.5 2 0.23 Blue * . . Co(NN)SO4 -S H2O 15.71 25.60 15.63 25.50 Pink 3 Ni(NN)SO4 -4 H2O 16.45 26.91 16.26 27.07 Green 3 Mn(NN)SO4 -S H2O 14.80 25.88 14.94 25.91 White 9 Ag2 (NN)2 SO4 37.71 16.79 37.56 16.83 White 53 a M = m e ta l . ^ A - an ion . c The co ndu c t iv i t ie s were m easu red in ab so lu te m e th ano l . 103 Table XXVI Cu(NN)2(OAc) Cu(NN)(OAc)2 Co(NN)2(OAc) Ni(NN)2(OAc)2 a M = m e ta l . ^ ACETATE COMPLEXES ( % C a lc d . - X r -% Found C H Ma Ab C H M A 14.38 2 6.75 14.25 26.88 ZH 2O 18.27 33.95 18.41 34.14 C D i-H NT P OtcTTP 5.15 11.17 22.39 47.57 5.14 11.24 22.69 •4 H2O 47.18 5.15 11.53 23.19 47.17 5.36 11.36 2140 Conduct .C Color - (molar) cm^ mho Blue 21 Blue 20 Brownish- orange - ' 54 Green C on cn . M x lO 4 7.69 7.42 7.18 A= an io n . c The c o nd u c t iv i t ie s were ob ta in ed in a b so lu te methanol so lu t io n s . 104 LITERATURE CITED 1. R. L. Bodner and D. G. H end r ic k e r , In o rg . N u c l . C h em . L e t te r s , 6 , 421 (1970). 2 . D . G . H end ricker and R. L. 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