STRONG METAL-METAL COUPLING IN A DINUCLEAR (TERPYRIDINE)(BIPYRIDINE)RUTHENIUM MIXED-VALENCE COMPLEX INCORPORATING THE BRIDGING LIGAND 1,4-DICYANAMIDOBENZENE DIANION

被引：43

作者：

REZVANI, AR ^{[1
]}

EVANS, CEB ^{[1
]}

CRUTCHLEY, RJ ^{[1
]}

机构：

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

来源：

INORGANIC CHEMISTRY | 1995年 / 34卷 / 18期

关键词：

D O I：

10.1021/ic00122a016

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The complex, [{Ru(terpy)(bpy)}2(mu-dicyd)][PF6](2), where terpy = 2,2',2''-terpyridine, bpy = 2,2'-bipyridine, and dicyd(2-) = 1,4-dicyanamidobenzene dianion, has been synthesized and characterized by cyclic voltammetry and spectroelectrochemical methods. A quantitative absorption spectrum of the radical anion dicyd(.-) has also been determined. The mixed valence ion, [{Ru(terpy)(bpy)](2)(mu-dicyd)](3+) is strongly coupled with K-c = 2.7 x 10(7) and has an intervalence band at lambda = 1090 nm (epsilon(max) 3000 M(-1) cm(-1), <(nu)over bar>(1/2) = 1800 cm(-1)). The mixed-valence properties of this complex were compared to its ammine analogue [{(NH3)(5)Ru}(2)(mu-dicyd)](3+) and rationalized by the perturbation of spectator ligands on the interaction of ruthenium ions with the dicyd(2-) superexchange pathway. The dependence of intervalence oscillator strength on the nature of the mixed-valence complex was also discussed.

引用

页码：4600 / 4604

页数：5

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