METAL-TO-LIGAND CHARGE-TRANSFER SPECTRA OF SOME CHLORO-BRIDGED COMPLEXES OF RHODIUM(I) AND IRIDIUM(I)

被引:45
作者
EPSTEIN, RA
GEOFFROY, GL
KEENEY, ME
MASON, WR
机构
[1] PENN STATE UNIV,DEPT CHEM,UNIVERSITY PK,PA 16802
[2] NO ILLINOIS UNIV,DEKALB,IL 60115
关键词
D O I
10.1021/ic50192a062
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Electronic absorption and magnetic circular dichroism (MCD) spectra are reported for the chloro-bridged dimers [RhCl(CO)2]2, [RhCl(COD)]2, [RhCl(NBD)]2, and [IrCl(COD)]2 (COD=1, 5-cyclooctadiene; NBD=norbornadiene) in dichloromethane solution. Absorption spectra are also reported for the less stable [RhCl(C2H4)2]2, [RhCl(COT)2]2, and [IrCl(COT)2]2 (COT=cyclooctene) complexes. Spectra at 77 K were also obtained for [RhCl(CO)2]2 and several of the olefin complexes in glassy EPA or methylcyclohexane/pentane solution. Dissolution of [RhCl(CO)2]2, [RhCl(COD)]2, [RhCl(NBD)]2, and [IrCl(COD)]2 in acetonitrile gives a bridge-cleavage reaction, and spectral data are reported for the monomeric products [RhCl(CO)2(CH3CN)], [RhCl(COD)(CH3CN)], [RhCl(NBD)(CH3CN)], and [IrCl(COD)(CH3CN)]. The intense bands observed in the visible and near-ultraviolet regions of the spectra of all these complexes are assigned as metal-to-ligand charge-transfer (MLCT) transitions from occupied metal d orbitals to low-energy ligand À orbitals. Detailed spectral assignments are presented, and comparisons are made between the chloro-bridged complexes and related monomeric complexes. © 1979, American Chemical Society. All rights reserved.
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页码:478 / 484
页数:7
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