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Published on: March 12, 2015
Characterization of a diferrous terminal hydride mechanistically relevant to the Fe-only hydrogenases
Jarl Ivar van der Vlugt1, Thomas B Rauchfuss, C Matthew Whaley
1Department of Chemistry, University of Illinois at Urbana--Champaign, Urbana, Illinois 61801, USA.
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.
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