title: Characterization of a diferrous terminal hydride mechanistically relevant to the Fe-only hydrogenases.
abstract: Reduction of diferrous dithiolato complexes with hydride donor reagents affords the first example of the previously elusive terminal diferrous hydride, [Fe2(edt)(mu-CO)(H)(CO)(PMe3)4]PF6 (edt = S2C2H4). Crystallographic characterization shows that this model contains an asymmetrical semi-bridging CO trans to a terminal hydrido, as indicated in the Hred state in the D. desulfuricans enzyme. The model reacts with protons to yield H2 and rearranges via an intramolecular process to the isomeric mu-hydrido isomer, which is unreactive toward protons.
authors.affiliation: Department of Chemistry, University of Illinois at Urbana--Champaign, Urbana, Illinois 61801, USA.
authors.forename: Jarl Ivar
authors.initials: JI
authors.lastname: van der Vlugt
authors.forename: Thomas B
authors.initials: TB
authors.lastname: Rauchfuss
authors.forename: C Matthew
authors.initials: CM
authors.lastname: Whaley
authors.forename: Scott R
authors.initials: SR
authors.lastname: Wilson
mesh_terms: D005296:Ferrous Compounds / Q000737:chemistry* / Q000378:metabolism*; D006859:Hydrogen / Q000737:chemistry / Q000378:metabolism*; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism*; D007501:Iron / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism*; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D017550:Spectroscopy, Fourier Transform Infrared
chemical_list: D005296:Ferrous Compounds; D007506:Iron-Sulfur Proteins; D006859:Hydrogen; D007501:Iron; C118830:iron hydrogenase; D006864:Hydrogenase