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

Seiji Ogo, Ryota Kabe, Hideki Hayashi, Ryosuke Harada, Shunichi Fukuzumi

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Abstract

Ruthenium aqua complexes [(η6-C6Me 6)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 CO 2 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.

Original languageEnglish
Pages (from-to)4657-4663
Number of pages7
JournalDalton Transactions
Issue number39
DOIs
Publication statusPublished - Oct 12 2006

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Hydrogenation
Hydrides
Catalysts
Iridium
Ruthenium
Hydrogen
Carbon Monoxide
Kinetics

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

@article{ff69365575634407aaa269a3b9c6cb34,
title = "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",
abstract = "Ruthenium aqua complexes [(η6-C6Me 6)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 CO 2 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.",
author = "Seiji Ogo and Ryota Kabe and Hideki Hayashi and Ryosuke Harada and Shunichi Fukuzumi",
year = "2006",
month = "10",
day = "12",
doi = "10.1039/b607993h",
language = "English",
pages = "4657--4663",
journal = "Dalton Transactions",
issn = "1477-9226",
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T1 - Mechanistic investigation of CO2 hydrogenation by Ru(ii) and Ir(iii) aqua complexes under acidic conditions

T2 - Two catalytic systems differing in the nature of the rate determining step

AU - Ogo, Seiji

AU - Kabe, Ryota

AU - Hayashi, Hideki

AU - Harada, Ryosuke

AU - Fukuzumi, Shunichi

PY - 2006/10/12

Y1 - 2006/10/12

N2 - Ruthenium aqua complexes [(η6-C6Me 6)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 CO 2 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.

AB - Ruthenium aqua complexes [(η6-C6Me 6)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 CO 2 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.

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