Reversible Heterolysis of H2 Mediated by an M−S(Thiolate) Bond (M = Ir, Rh): A Mechanistic Implication for [NiFe] Hydrogenase

Reversible Heterolysis of H2 Mediated by an M−S(Thiolate) Bond (M = Ir, Rh): A Mechanistic Implication for [NiFe] Hydrogenase

Facile H2 heterolysis was found to be mediated by coordinatively unsaturated Cp*Ir and Cp*Rh thiolate complexes. The reaction of iridium complex is reversible, and the formation of an intermediary Ir−H/thiol complex was detected. The reversible conversion between thiolate complex+H2 and hydride comp...

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Veröffentlicht in:Journal of the American Chemical Society 2008-09, Vol.130 (35), p.11610-11611
Hauptverfasser: Ohki, Yasuhiro, Sakamoto, Mayumi, Tatsumi, Kazuyuki
Format: Artikel
Sprache:eng
Schlagworte:
Binding Sites
Deuterium - chemistry
Hydrogen - chemistry
Hydrogen - metabolism
Hydrogenase - chemistry
Hydrogenase - metabolism
Iridium - chemistry
Rhodium - chemistry
Sulfhydryl Compounds - chemistry
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Zusammenfassung:Facile H2 heterolysis was found to be mediated by coordinatively unsaturated Cp*Ir and Cp*Rh thiolate complexes. The reaction of iridium complex is reversible, and the formation of an intermediary Ir−H/thiol complex was detected. The reversible conversion between thiolate complex+H2 and hydride complex+thiol provides an intriguing functional model of [NiFe] hydrogenase.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja804848w