Electron transfer properties of rhodium(I) oxalate complexes

J. E. Anderson; C. P. Murphy; J. Real; J. Balué; J. C. Bayón

doi:10.1016/S0020-1693(00)85136-1

Electron transfer properties of rhodium(I) oxalate complexes

J. E. Anderson, C. P. Murphy, J. Real, J. Balué, J. C. Bayón

Department of Chemistry

Research output: Contribution to journal › Article › Research › peer-review

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Abstract

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. © 1993.

Original language	English
Pages (from-to)	151-160
Journal	Inorg. Chim. Acta
Volume	209
Issue number	2
DOIs	https://doi.org/10.1016/S0020-1693(00)85136-1
Publication status	Published - 15 Jul 1993

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@article{f6962df6e1ea49288610a5c77ac478d4,

title = "Electron transfer properties of rhodium(I) oxalate complexes",

abstract = "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. {\textcopyright} 1993.",

author = "Anderson, {J. E.} and Murphy, {C. P.} and J. Real and J. Balu{\'e} and Bay{\'o}n, {J. C.}",

year = "1993",

month = jul,

day = "15",

doi = "10.1016/S0020-1693(00)85136-1",

language = "English",

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pages = "151--160",

journal = "Inorg. Chim. Acta",

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TY - JOUR

T1 - Electron transfer properties of rhodium(I) oxalate complexes

AU - Anderson, J. E.

AU - Murphy, C. P.

AU - Real, J.

AU - Balué, J.

AU - Bayón, J. C.

PY - 1993/7/15

Y1 - 1993/7/15

N2 - 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. © 1993.

AB - 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. © 1993.

U2 - 10.1016/S0020-1693(00)85136-1

DO - 10.1016/S0020-1693(00)85136-1

M3 - Article

SN - 0020-1693

VL - 209

SP - 151

EP - 160

JO - Inorg. Chim. Acta

JF - Inorg. Chim. Acta

IS - 2

ER -

Electron transfer properties of rhodium(I) oxalate complexes

Abstract

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