title: An S-Oxygenated [NiFe] Complex Modelling Sulfenate Intermediates of an O2-Tolerant Hydrogenase.
abstract: To understand the molecular details of O2-tolerant hydrogen cycling by a soluble NAD+-reducing [NiFe] hydrogenase, we herein present the first bioinspired heterobimetallic S-oxygenated [NiFe] complex as a structural and vibrational spectroscopic model for the oxygen-inhibited [NiFe] active site. This compound and its non-S-oxygenated congener were fully characterized, and their electronic structures were elucidated in a combined experimental and theoretical study with emphasis on the bridging sulfenato moiety. Based on the vibrational spectroscopic properties of these complexes, we also propose novel strategies for exploring S-oxygenated intermediates in hydrogenases and similar enzymes.
authors.affiliation: Institut für Chemie: Metallorganik und Anorganische Materialien, Sekr. C2, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Nils J
authors.initials: NJ
authors.lastname: Lindenmaier
authors.affiliation: Institut für Chemie: Physikalische Chemie/Biophysikalische Chemie, Sekr. PC14, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Wahlefeld
authors.affiliation: Abteilung Molekulare Theorie und Spektroskopie, Max-Planck-Institut für Chemische Energiekonversion, Mülheim a. d. Ruhr, Germany.
authors.forename: Eckhard
authors.initials: E
authors.lastname: Bill
authors.affiliation: Department of Chemical and Biological Engineering, University of Wisconsin, Madison, USA.
authors.forename: Tibor
authors.initials: T
authors.lastname: Szilvási
authors.affiliation: Institut für Chemie: Metallorganik und Anorganische Materialien, Sekr. C2, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Christopher
authors.initials: C
authors.lastname: Eberle
authors.affiliation: Institut für Chemie: Metallorganik und Anorganische Materialien, Sekr. C2, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Shenglai
authors.initials: S
authors.lastname: Yao
authors.affiliation: Institut für Chemie: Physikalische Chemie/Biophysikalische Chemie, Sekr. PC14, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Peter
authors.initials: P
authors.lastname: Hildebrandt
authors.affiliation: Institut für Chemie: Physikalische Chemie/Biophysikalische Chemie, Sekr. PC14, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Marius
authors.initials: M
authors.lastname: Horch
authors.affiliation: Institut für Chemie: Physikalische Chemie/Biophysikalische Chemie, Sekr. PC14, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Ingo
authors.initials: I
authors.lastname: Zebger
authors.affiliation: Institut für Chemie: Metallorganik und Anorganische Materialien, Sekr. C2, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Matthias
authors.initials: M
authors.lastname: Driess
mesh_terms: D020134:Catalytic Domain; D018360:Crystallography, X-Ray; D020118:Cupriavidus necator / Q000737:chemistry / Q000201:enzymology*; D006864:Hydrogenase / Q000737:chemistry*; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013059:Spectrum Analysis, Raman
chemical_list: C043296:nickel-iron hydrogenase; D006864:Hydrogenase; D010100:Oxygen
keywords: IR spectroscopy; [NiFe] hydrogenases; enzyme models; resonance Raman spectroscopy; spectroscopic models