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    Please use this identifier to cite or link to this item: http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/104688


    Title: A Reduced 2Fe2S Cluster Probe of Sulfur-​Hydrogen versus Sulfur-​Gold Interactions
    Authors: Crouthers, Danielle J.;Ding, Shengda;Denny, Jason A.;Bethel, Ryan D.;Hsieh, Chung-Hung;Hall, Michael B.;Darensbourg, Marcetta Y
    Keywords: Fe-S-Au-Cluster;Hydrogenasen;Hydrosulfide;Isolobale Spezies;Schwefelinversion
    Date: 2015-09-14
    Issue Date: 2016-01-06 11:07:15 (UTC+8)
    Publisher: Wiley - V C H Verlag GmbH & Co. KGaA
    Abstract: The Ph3PAu+ cation, renowned as an isolobal analogue of H+, was found to serve as a proton surrogate and form a stable Au2Fe2 complex, [(μ-SAuPPh3)2{Fe(CO)3}2], analogous to the highly reactive dihydrosulfide [(μ-SH)2{Fe(CO)3}2]. Solid-state X-ray diffraction analysis found the two SAuPPh3 and SH bridges in anti configurations. VT NMR studies, supported by DFT computations, confirmed substantial barriers of approximately 25 kcal mol−1 to intramolecular interconversion between the three stereoisomers of [(μ-SH)2{Fe(CO)3}2]. In contrast, the largely dative S[BOND]Au bond in μ-SAuPPh3 facilitates inversion at S and accounts for the facile equilibration of the SAuPPh3 units, with an energy barrier half that of the SH analogue. The reactivity of the gold-protected sulfur atoms of [(μ-SAuPPh3)2{Fe(CO)3}2] was accessed by release of the gold ligand with a strong acid to generate the [(μ-SH)2{Fe(CO)3}2] precursor of the [FeFe]H2ase-active-site biomimetic [(μ2-SCH2(NR)CH2S){Fe(CO)3}2].
    Relation: Angewandte Chemie 127(38), pp.11254–11258
    DOI: 10.1002/ange.201504574
    Appears in Collections:[化學學系暨研究所] 期刊論文

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