SOLVENT DEPENDENCE OF LIGAND TO METAL CHARGE-TRANSFER OSCILLATOR STRENGTH - OUTER-SPHERE PERTURBATION OF THE RUTHENIUM(III)-CYANAMIDE BOND

被引：36

作者：

SALEH, AA ^{[1
]}

CRUTCHLEY, RJ ^{[1
]}

机构：

[1] CARLETON UNIV,OTTAWA CARLETON CHEM INST,OTTAWA K1S 5B6,ONTARIO,CANADA

来源：

INORGANIC CHEMISTRY | 1990年 / 29卷 / 11期

关键词：

D O I：

10.1021/ic00336a019

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A study of the effect of the nature of the solvent on the b1* → b1] LMCT oscillator strength of the complex [(NH3)5Ru((2,3-dichlorophenyl)cyanamide(1-))][ClO4]2 is reported. A plot of LMCT oscillator strength vs donor number gives a linear relationship with intercept 0.186, slope -0.00294/DN, and R = 0.998. Weak and strong coupling approaches to donor and acceptor interactions are used to evaluate this novel effect. The strong coupling approach, in which oscillator strength is proportional to the square of the donor and acceptor wave function overlap, appears to be consistent with all experimental data. Thus, the outer-sphere hydrogen-bonding interactions of the donor solvent with the ammine protons perturbs the ruthenium(III) π-acceptor wave function, reducing its overlap with the π-donor wave function of the cyanamide group. © 1990, American Chemical Society. All rights reserved.

引用

页码：2132 / 2135

页数：4

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