title: Synthesis, Characterization, and Reactivity of Functionalized Trinuclear Iron-Sulfur Clusters - A New Class of Bioinspired Hydrogenase Models.
abstract: The air- and moisture-stable iron-sulfur carbonyl clusters Fe3S2(CO)7(dppm) (1) and Fe3S2(CO)7(dppf) (2) carrying the bisphosphine ligands bis(diphenylphosphanyl)methane (dppm) and 1,1'-bis(diphenylphosphanyl)ferrocene (dppf) were prepared and fully characterized. Two alternative synthetic routes based on different thionation reactions of triiron dodecacarbonyl were tested. The molecular structures of the methylene-bridged compound1and the ferrocene-functionalized derivative2were determined by single-crystal X-ray diffraction. The catalytic reactivity of the trinuclear iron-sulfur cluster core for proton reduction in solution at low overpotential was demonstrated. These deeply colored bisphosphine-bridged sulfur-capped iron carbonyl systems are discussed as promising candidates for the development of new bioinspired model compounds of iron-based hydrogenases.
authors.affiliation: Institute of Inorganic Chemistry, Johannes Kepler University Linz (JKU) , Altenbergerstr. 69, 4040 Linz, Austria , http://www.anorganik.jku.at.
authors.forename: Manuel
authors.initials: M
authors.lastname: Kaiser
authors.affiliation: Institute of Inorganic Chemistry, Johannes Kepler University Linz (JKU) , Altenbergerstr. 69, 4040 Linz, Austria , http://www.anorganik.jku.at.
authors.forename: Günther
authors.initials: G
authors.lastname: Knör
keywords: Bioinspired catalysis; Cluster compounds; Enzyme models; Hydrogenase; Iron; ­Carbonyl ligands