SUBSTITUENT EFFECTS AND BONDING CHARACTERISTICS IN (O-BENZOQUINONE DIIMINE)BIS(BIPYRIDINE)RUTHENIUM(II) COMPLEXES

被引：101

作者：

MASUI, H ^{[1
]}

LEVER, ABP ^{[1
]}

DODSWORTH, ES ^{[1
]}

机构：

[1] YORK UNIV,DEPT CHEM,N YORK M3J 1P3,ON,CANADA

来源：

INORGANIC CHEMISTRY | 1993年 / 32卷 / 03期

关键词：

D O I：

10.1021/ic00055a005

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The effect of substituents on the electrochemistry and electronic spectroscopy of Ru(II)(bpy)2LL complexes is reported, where bpy = 2,2'-bipyridine and LL = 4,5-disubstituted o-benzoquinone diimines, o-semiquinone diimines, o-benzenediamides, and o-phenylenediamines. These data are used to create a map of the orbital energies as a function of the Hammett parameter of the substituents, giving insight into the electronic behavior of these complexes. Electronic spectra are characterized with respect to energy, intensity, and bandwidth, and bands are assigned with support from resonance Raman (rR) and FTIR data. The solvatochromism of the o-benzoquinone diimine species is discussed. The data are interpreted in the context of metal-ligand orbital mixing and electronic structure. An ab initio study of the uncomplexed ligand in its quinone diimine oxidation state is also included.

引用

页码：258 / 267

页数：10

共 68 条

[1] SYNTHESIS AND SPECTROSCOPIC CHARACTERIZATION OF BIS[BIS(BIPYRIDINE)RUTHENIUM(II)] 3,3',4,4'-TETRAIMINO-3,3',4,4'-TETRAHYDROBIPHENYL AND ITS REDOX PRODUCTS [J].