PH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases

Bunsho Kure; Takahiro Matsumoto; Koji Ichikawa; Shunichi Fukuzumi; Yoshiki Higuchi; Tatsuhiko Yagi; Seiji Ogo

doi:10.1039/b807555g

PH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases

Bunsho Kure, Takahiro Matsumoto, Koji Ichikawa, Shunichi Fukuzumi, Yoshiki Higuchi, Tatsuhiko Yagi, Seiji Ogo

Department of Chemistry & Nanoscience

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

36 Scopus citations

Abstract

The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(μ-thiolate)(μ-hydride)NiRu complexes, Ni^II(μ-SR)₂(μ-H)Ru^II {(μ-SR)₂ = N,N′-dimethyl-N,N′-bis(2-mercaptoethyl)-1, 3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the μ-H ligand of the Ni^II(μ-SR) ₂(μ-H)Ru^II complexes has H⁺ properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni^I(μ-SR)₂Ru^I complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the μ-H ligand of the Ni ^II(μ-SR)₂(μ-H)Ru^II complexes acts as H^-, and the complexes catalyse the hydrogenation of carbonyl compounds.

Original language	English
Pages (from-to)	4747-4755
Number of pages	9
Journal	Dalton Transactions
Issue number	35
DOIs	https://doi.org/10.1039/b807555g
State	Published - 2008

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@article{cb35d4404b534716a92e77506c77cf02,

title = "PH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases",

abstract = "The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(μ-thiolate)(μ-hydride)NiRu complexes, NiII(μ-SR)2(μ-H)RuII {(μ-SR)2 = N,N′-dimethyl-N,N′-bis(2-mercaptoethyl)-1, 3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the μ-H ligand of the NiII(μ-SR) 2(μ-H)RuII complexes has H+ properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent NiI(μ-SR)2RuI complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the μ-H ligand of the Ni II(μ-SR)2(μ-H)RuII complexes acts as H-, and the complexes catalyse the hydrogenation of carbonyl compounds.",

author = "Bunsho Kure and Takahiro Matsumoto and Koji Ichikawa and Shunichi Fukuzumi and Yoshiki Higuchi and Tatsuhiko Yagi and Seiji Ogo",

year = "2008",

doi = "10.1039/b807555g",

language = "English",

pages = "4747--4755",

journal = "Dalton Transactions",

issn = "1477-9226",

number = "35",

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TY - JOUR

T1 - PH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases

AU - Kure, Bunsho

AU - Matsumoto, Takahiro

AU - Ichikawa, Koji

AU - Fukuzumi, Shunichi

AU - Higuchi, Yoshiki

AU - Yagi, Tatsuhiko

AU - Ogo, Seiji

PY - 2008

Y1 - 2008

N2 - The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(μ-thiolate)(μ-hydride)NiRu complexes, NiII(μ-SR)2(μ-H)RuII {(μ-SR)2 = N,N′-dimethyl-N,N′-bis(2-mercaptoethyl)-1, 3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the μ-H ligand of the NiII(μ-SR) 2(μ-H)RuII complexes has H+ properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent NiI(μ-SR)2RuI complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the μ-H ligand of the Ni II(μ-SR)2(μ-H)RuII complexes acts as H-, and the complexes catalyse the hydrogenation of carbonyl compounds.

AB - The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(μ-thiolate)(μ-hydride)NiRu complexes, NiII(μ-SR)2(μ-H)RuII {(μ-SR)2 = N,N′-dimethyl-N,N′-bis(2-mercaptoethyl)-1, 3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the μ-H ligand of the NiII(μ-SR) 2(μ-H)RuII complexes has H+ properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent NiI(μ-SR)2RuI complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the μ-H ligand of the Ni II(μ-SR)2(μ-H)RuII complexes acts as H-, and the complexes catalyse the hydrogenation of carbonyl compounds.

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U2 - 10.1039/b807555g

DO - 10.1039/b807555g

M3 - Article

C2 - 18728883

AN - SCOPUS:50249141733

SN - 1477-9226

SP - 4747

EP - 4755

JO - Dalton Transactions

JF - Dalton Transactions

IS - 35

ER -

PH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases

Abstract

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