ELECTRON-TRANSFER PROPERTIES OF RHODIUM(I) OXALATE COMPLEXES

被引：6

作者：

ANDERSON, JE ^{[1
]}

MURPHY, CP ^{[1
]}

REAL, J ^{[1
]}

BALUE, J ^{[1
]}

BAYON, JC ^{[1
]}

机构：

[1] UNIV AUTONOMA BARCELONA, DEPT QUIM, E-08193 BARCELONA, SPAIN

来源：

INORGANICA CHIMICA ACTA | 1993年 / 209卷 / 02期

关键词：

D O I：

10.1016/S0020-1693(00)85136-1

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis, electrochemical and spectroelectrochemical properties of (TMA)[Rh(OX)(CO)2], (TMA)[Rh(ox)(COD)] and [Rh2(OX)(COD)2], where TMA is tetramethylammonium, COD is 1,5-cyclooctadiene and ox is oxalate dianion, are reported. The monometallic complexes, (TMA)[Rh(ox)(CO)2] and (TMA)[Rh(ox)(COD)], can be oxidized by two electrons. However their oxidation is followed by a chemical reaction to form a solvated Rh complex and two equivalents of CO2 due to decomposition of the oxalate. The bimetallic complex, [Rh2(ox)(COD)2], is oxidized electrochemically in two successive two-electron steps without decomposition of the coordinated oxalate. An equilibrium reaction between [Rh(ox)(COD)]-, [Rh(COD)(CH3CN)2]+ and [Rh2(COD)2(ox)] is present which complicates the electron transfer mechanism. Chemical oxidations of (TMA)[Rh(ox)(COD)] and [Rh2(ox)(COD)2] were performed to further establish the products of the oxidation reactions and the formation of [Rh2(CH3CN)(COD)2(ox)]BF4 is reported.

引用

页码：151 / 160

页数：10

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