Russian Chemical Butletm. International Edition, k?d. 49, No. II. November. 2000
t863
Organometallic Chemistry Synthesis, structures, and spectral properties of biomimetic azomethine metal chelates with chromophores CuN2S 2, CuNzO2, and CuN2Se 2. Crystal structure of bis[4-(benzyi)aldimino-3-methyl- l-phenyl-5-pyrazolothiolato]copper(~l) A. I. UraevJ' A. L. Nivoro-,.hMn, h G. I. Bondarenko. '~ K. A. Ly.senko, ~'*" O. Yu. Korshunov," K G. ~Tasenko," A. T. Shuvaev, a V. P. Kurbatov, u M. Yu. Antipin," a n d A. D. Garner.skiP
"Re.s/or 5)eye O)m,eJ:sit.v, 194/'2 prosp. Stachki. 344090 Roster-on- Don, Russian Federalion. Fax: +7 (883 22 2S 5007. E-mad:
[email protected] rtt ~ftarvard Univers;ty, Boston. US"A. if-mail: a/exnivg3'.sancttmo'.llarvard.edtt L,I. N. Ne.smm'anov /it.sligt;le of O~anoe/ement Compounds. Russian Academy of Science~. 28 ul. 6.;vilova, / ] 7b'/.? Me.scow, R,ts,sian Federation, Fax: .-r 7 (095) 135 5085. E-moil: koso'
[email protected] Copper(iO chelate:, of compositiolt Cul_.~ \sere -,w~thcsizcd based o~3 a plcx 5a in the crystal occupies a s p e c i a l crystallograpific p o s i t i o n on a t w o l b l d axes ( C 2) passing tilrough thc Cu a t o m (Fig. I). The g e o m e t r y o f t h e b i d c m a t c ligand is
Ru.~s.Chem. Bull.. htt.Ed., Vol. 49, No. II. November. 2000
B i o m i m c t i c a z o m e t h i n e m e t a l chelates
TaMe I. Propcrtie,; of complexes 5 Corn-
pOIllld
Yield it}- )
N, Found
(%)
Molecular
C'atc tlhllcd
l'orlll klhl
_I~.~t j 12.43 10.85 10.91 13.1 I 13.04 _1~,9~ 1603 12.40 12.43
C .t>l-132NhS2Cu
5a
t>0
5b
7t
5e
65
54
69
5e
72
5f
63
.[.~,.I.8 13.03
(:~ tl 4N,sS2Cu
58
7(1
C241t22N682Cu
5h
64
1.5.r 16.09 .!~3:7.2_
C~al|;2 N,>Sc2Cu C ~,il32 N0()?Cu C241t 2.1N ~,S_.].Cu C ;t, t132N6g2Cu
C'2aI t ?2N6So2Cu
13.64 5k
69
51
7l)
5m
(,:~
[,}.8~ 14.93 _!.3.2_4 1327
C4oH ~oN,~S2Cu C 4 ~lt ~tlNxSc?Cu (' ~.~H ~2 N sS 2Cu
!_5_,~.9
15.64
1805
c h a r a c t e r i z e d by values typical o f this class o f c o m pounds. 14 As e x p e c t e d , 15 the Cu a t o m in this c h e l a t e is in a distorted t e t r a h e d r a l tig:lnd c n v i r o n m c l l i o f the N2S 2 type. The S( I ) - - ( ; t i t I ) - - - N ( I ) and St I I - - O i l I i - - N ( I A ) b o n d angles tire 1 0 0 . 7 4 ( 9 ) a n d 134.25(9J ~ rcspectivel.,,. The dihedral angle b e t w e e n the N C u S planes o f two c o o r d i n a t i o n units is 60..qo , which is s o m e w h a t larger t h a n that in c o m p l e x 3 t57.6~ i5 T h e C u - - N a n d C u - - S b o n d lengths in 5a ( I . 9 8 2 ( 3 ) and 2.2497(11) ,-~. respectively) are close to the c o r r e s p o n d i n g values in o t h e r four-coordinate m e t a l c h e l a t e s o f Cu II w i t h the N . S - l i g a n d e n v i r o n m e n t 14 (see Table 2). T h e C u - - N and C u . - S b o n d tcngths in "blue" c o p p e r p r o t e i n s are in . u , - - , .~ ", ,'i. respectively. '~ the ranues o f I . 99 - - ). .15 . a n. d ~ "" These values arc substantially smaller t h a n the corres p o n d i n g p a r a m e t e r s o b s e r v e d in b i o m i m c t i c c o m plexes. 14 T h e iris p.vrazolyl)borate c o m p l e x o f type I is the onl,, c x a m p t e I~ o f model c o m p o t m d s in w h i c h the cqually short C u - - S b o n d is observed. It s h o u l d be n o t e d that chelate 5a is the secc)nd example of c o m p l c x e s with the CuN2S 2 c h r o m o p h o r c possessing an opcll structure. which was c h a r a c t e r i z c d by X-ray diffraction dat:l (q's Ref~. 9. 14. a n d 15). ]'tic structural data for the nearest erp,,ironmct~t ;.lbOtlt the Cu a t o m s in c h e l a t e s 5 a - - e , k were o b t a i n e d by
Table 2. The Cu--X arm C u - - N bond lengths (d) dctcrmiuu'd by X-r:iy dif(rzlclion al'~alvsis and [-XAFS ~,pcclro,,cop.~, the p:uamcters oI the s !CHCI 3. 77 Ki and UV ICHCI;I spccirzl. :uld lhc magnclic inonicnt,; of coral)loxes 3 and 5 Cornl'lG'ulld
d/.& Ctl-X
ESR ,;pccirum Cu--N
,gi,
"-'i
g,
/1!1" 10-4
"It" 10-a
UV 'ff)ectrum
Pc'l
/':nax (fcicn.l-i nlol-i)
.,'laB
CFII-- i
3 5a
.....0 1") / .._4~
1.982 1.982
2.149 2.153
2.030 2.040
2.076 2.074
131.3 136 l
50.4
574 t 1240)
1.8
52.4
710 (960) 556 (181S)
1.76
1.97" 56 5c 5,1
.96 ~
2.05*
5e
2.136
2t.)37
2.091
131.8
63.1
2.234 2.152
2.063 2.058
2.119 2.1+!2
143.5 137.0
51.1 67 0
2. 152
2.!)41
2.072
137.{5
5+).4
700 554 724 468 544 ,580 590
(14821 (1010) ( II)00i (1155) ( 1980} i 1470) (24401
1.78 1.81 1.73 1.78
700 (2040) 5f
2.150
2.036
5g
2.123
2.049
5h
5k
51
2 30*
2.02*
244"
2.63" 2 04* 2.50 +
5m
2.076
136.1
71.3
183.7
2.11)6
2.O46
2.06(~
1879
87.2
2.138 2158 *+ 2.10(;
2.047
2.(i86 2.082 ~* 2.064
< li) N 4 > N2S 2 ISCe Ref. 9). The ESR characteristics o f " c o m p l e x c s 5a--f differ substantially from those o f natural compottnds. 3-n As can be semi fronl Table 2. parameters of the ESR spectra similar to those of "blue" c o p p e r proteins were achieved by introducing the quinoline R substituent into the a m i u e l'ragrnent of chelates 5 (compounds 5k--m). Apparently, a considerable effect o f this substitu0nt on the parameters of the ESR spectra of complexes 5 is :attributable to an additional coordination of the N atom of the quinoline [ragmcnt (Gt] Rels. 24 and 25), the distortion o f the chelat0 u n i l , and ;.I c h a n g e in l h c e l ] ] c i c l / c y o f o v e r l a p p i i l g oi" the a t o m i c o r b i t a l s , were iliC:,lStllcd Oll :111 atllOlll;lled Ibtlr-circle Sit_'Fllell5 P3IPC dit'iractometcr at 2'J~ K (NhI-Kc~ radialion. graphite n l o n o c h r o l l l a t o r , 0/20 scanning t e c h n i q u e . 20ma x = 50 chniquex]. 19~,S. 3. 234 (in Russianl. 29. S. 1. Zabenski, .I J Rclir, A. AllcudillOV. R. C. Albcrs, ;.lild M. J. EIIoi', Ph)'.~. Roy. 52.. 2995. 30. G. M. Sheldrick, S t f E L X T L Phl.s. PC' Fk,rwol~. A. ,Sy,~'h'm q/ Computer Program.x jbr file Detertltitlation of CO:Mal SIFttctr ]ram X-Ray Dijfi'ucmm Dam. Rev. 502, Siclncns Analitic:ll X-ray Inslrumcnts him., Germany 1994. 31 B. A. t)orai-Ko~hii~ :rod I. '(a. Kvitko. Zh. Oh.shch Khim.. 1962. 32.. 405!) Id. Gen. Chem. USSR, 1902. 32 IEn~! r,ansl.)l.
Received Junuarv ~r 2#00: /el revisedj(~t'tn May 1o. 20()0
