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Dalton Transactions

The international journal for inorganic, organometallic and bioinorganic chemistry



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Dalton Trans., 2008, 4747 - 4755, 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 and Seiji Ogo

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(-thiolate)(-hydride)NiRu complexes, NiII(-SR)2(-H)RuII {(-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 -H ligand of the NiII(-SR)2(-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(-SR)2RuI complex is proposed. In contrast, in neutral–basic media (at pH 7–10), the -H ligand of the NiII(-SR)2(-H)RuII complexes acts as H-, and the complexes catalyse the hydrogenation of carbonyl compounds.

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