title: Reversible heterolysis of H2 mediated by an M-S(thiolate) bond (M = Ir, Rh): a mechanistic implication for [NiFe] hydrogenase.
abstract: 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.
authors.affiliation: Department of Chemistry and Graduate School of Science and Research Center for Meterials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan. ohki@mbox.chem.nagoya-u.ac.jp
authors.forename: Yasuhiro
authors.initials: Y
authors.lastname: Ohki
authors.forename: Mayumi
authors.initials: M
authors.lastname: Sakamoto
authors.forename: Kazuyuki
authors.initials: K
authors.lastname: Tatsumi
mesh_terms: D001665:Binding Sites; D003903:Deuterium / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry* / Q000378:metabolism; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007495:Iridium / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D013438:Sulfhydryl Compounds; D007495:Iridium; D006859:Hydrogen; D003903:Deuterium; D012238:Rhodium; C043296:nickel-iron hydrogenase; D006864:Hydrogenase