SOLVENT TRAPPED VALENCY IN THE [BIS(PENTAAMMINERUTHENIUM)(MU-1,4-DICYANAMIDOBENZENE)] TRICATION

被引：26

作者：

NAKLICKI, ML ^{[1
]}

CRUTCHLEY, RJ ^{[1
]}

机构：

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

来源：

INORGANICA CHIMICA ACTA | 1994年 / 225卷 / 1-2期

关键词：

MIXED VALENCE COMPLEX; ELECTROCHEMISTRY; RUTHENIUM COMPLEXES; AMMINE COMPLEXES; DICYANAMIDO COMPLEXES;

D O I：

10.1016/0020-1693(94)04038-9

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Cyclic voltammetry measurements show an unprecedented solvent dependence of metal-metal coupling for the symmetric mixed valence [3,2] complex, [{(NH3)(5)Ru}(2)(mu-dicyd)](3+), where dicyd(2-) is the 1,4-dicyanamidobenzene dianion. The comproportionation constant was determined to be K-c = 10 and 68 400 in aqueous and acetonitrile solution, respectively, The intervalence absorption band was deconvoluted from the low energy Ru(IIl)-cyanamide LMCT band by curve fitting analysis which gave for the [3,2] complex assuming a gaussian IT band, E(op) = 8190 cm(-1), Delta $($) over bar$$nu(1/2) = 4090 cm(-1) and epsilon(max) = 2590 M(-1) cm(-1) in aqueous solution and in acetonitrile solution E(op) = 6910 cm(-1), Delta $($) over bar$$nu(1/2) = 2640 cm(-1) and epsilon(max) = 19 400 M(-1) cm(-1). It is suggested that donor-acceptor interactions between the solvent and ammine protons weakens the Ru(III)-cyanamide pi bond. Because the interaction between Ru(III) and the cyanamide group is crucial to superexchange, metal-metal coupling is also weakened. The acceptor properties of water may also play a role.

引用

页码：123 / 127

页数：5

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