Issue 39, 2006

Mechanistic investigation of CO2hydrogenation by Ru(ii) and Ir(iii) aqua complexes under acidic conditions: two catalytic systems differing in the nature of the rate determining step

Abstract

Ruthenium aqua complexes [(η6-C6Me6)RuII(L)(OH2)]2+ {L = bpy (1) and 4,4′-OMe-bpy (2), bpy = 2,2′-bipyridine, 4,4′-OMe-bpy = 4,4′-dimethoxy-2,2′-bipyridine} and iridium aqua complexes [Cp*IrIII(L)(OH2)]2+ {Cp* = η5-C5Me5, L = bpy (5) and 4,4′-OMe-bpy (6)} act as catalysts for hydrogenation of CO2 into HCOOH at pH 3.0 in H2O. The active hydride catalysts cannot be observed in the hydrogenation of CO2 with the ruthenium complexes, whereas the active hydride catalysts, [Cp*IrIII(L)(H)]+ {L = bpy (7) and 4,4′-OMe-bpy (8)}, have successfully been isolated after the hydrogenation of CO2 with the iridium complexes. The key to the success of the isolation of the active hydride catalysts is the change in the rate-determining step in the catalytic hydrogenation of CO2 from the formation of the active hydride catalysts, [(η6-C6Me6)RuII(L)(H)]+, to the reactions of [Cp*IrIII(L)(H)]+ with CO2, as indicated by the kinetic studies.

Graphical abstract: Mechanistic investigation of CO2 hydrogenation by Ru(ii) and Ir(iii) aqua complexes under acidic conditions: two catalytic systems differing in the nature of the rate determining step

Supplementary files

Article information

Article type
Paper
Submitted
05 jun 2006
Accepted
01 aug 2006
First published
16 aug 2006

Dalton Trans., 2006, 4657-4663

Mechanistic investigation of CO2 hydrogenation by Ru(II) and Ir(III) aqua complexes under acidic conditions: two catalytic systems differing in the nature of the rate determining step

S. Ogo, R. Kabe, H. Hayashi, R. Harada and S. Fukuzumi, Dalton Trans., 2006, 4657 DOI: 10.1039/B607993H

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