Pulsed ENDOR and ESEEM study of [bis(maleonitriledithiolato)nickel]-:: An investigation into the ligand electronic structure

被引:59
作者
Huyett, JE
Choudhury, SB
Eichhorn, DM
Bryngelson, PA
Maroney, MJ [1 ]
Hoffman, BM
机构
[1] Univ Massachusetts, Amherst, MA 01003 USA
[2] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA
关键词
D O I
10.1021/ic9703639
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
By a combination of Q-band pulsed ENDOR (electron nuclear double resonance) and X-band ESEEM (electron stimulated echo envelope modulation) techniques, we have determined the hyperfine tensors for ethylene (C1) and cyano (C2) carbons and N, of [Ni(mnt)(2)](-), along with the quadrupole tensor for nitrogen. These measurements give it electron spin densities of rho(C1) similar to 0.03 in the C1 2p(z) orbital, rho(C2) < 0.003, rho(N) similar to 0.01, such that in total, similar to 0.15 of the spin resides on the ligand atoms C and N, while the rest resides in the NiS4 core, giving rho(NiS4-) = 0.85. These results are compared with extended Huckel and density functional (BLYP) MO calculations, as well as with X alpha calculations reported earlier.
引用
收藏
页码:1361 / 1367
页数:7
相关论文
共 44 条
[1]  
Abragam A., 1970, ELECT PARAMAGNETIC R
[2]   INFRARED-DETECTABLE GROUPS SENSE CHANGES IN CHARGE-DENSITY ON THE NICKEL CENTER IN HYDROGENASE FROM CHROMATIUM-VINOSUM [J].
BAGLEY, KA ;
DUIN, EC ;
ROSEBOOM, W ;
ALBRACHT, SPJ ;
WOODRUFF, WH .
BIOCHEMISTRY, 1995, 34 (16) :5527-5535
[3]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[4]   NEW PULSE ENDOR TECHNIQUE [J].
DAVIES, ER .
PHYSICS LETTERS A, 1974, A 47 (01) :1-2
[5]   ESR STUDIES OF 4 COORDINATE COMPLEXES OF NICKEL,PALLADIUM AND PLATINUM RELATED BY ELECTRON TRANSFER REATIONS [J].
DAVISON, A ;
MAKI, AH ;
EDELSTEIN, N ;
HOLM, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1963, 85 (13) :2029-&
[6]   PREPARATION AND CHARACTERIZATION OF 4-COORDINATE COMPLEXES RELATED BY ELECTRON-TRANSFER REACTIONS [J].
DAVISON, A ;
HOLM, RH ;
EDELSTEIN, N ;
MAKI, AH .
INORGANIC CHEMISTRY, 1963, 2 (06) :1227-+
[7]  
Davison A., 1967, INORG SYNTH, V10, P8, DOI DOI 10.1002/9780470132418.CH3
[8]   Q-band pulsed electron spin-echo spectrometer and its application to ENDOR and ESEEM [J].
Davoust, CE ;
Doan, PE ;
Hoffman, BM .
JOURNAL OF MAGNETIC RESONANCE SERIES A, 1996, 119 (01) :38-44
[9]   JACK-BEAN UREASE (EC 3.5.1.5) - METALLOENZYME - SIMPLE BIOLOGICAL ROLE FOR NICKEL [J].
DIXON, NE ;
GAZZOLA, C ;
BLAKELEY, RL ;
ZERNER, B .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1975, 97 (14) :4131-4133
[10]   Nature and electronic structure of the Ni-X dinuclear center of Desulfovibrio gigas hydrogenase. Implications for the enzymatic mechanism [J].
Dole, F ;
Fournel, A ;
Magro, V ;
Hatchikian, EC ;
Bertrand, P ;
Guigliarelli, B .
BIOCHEMISTRY, 1997, 36 (25) :7847-7854