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    Please use this identifier to cite or link to this item: http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/104680


    Title: Regioselectivity in Ligand Substitution Reactions on Diiron Complexes Governed by Nucleophilic and Electrophilic Ligand Properties
    Authors: Bethel, Ryan D.;Crouthers, Danielle J.;Hsieh, Chung-Hung;Denny, Jason A.;Hall, Michael B.;Darensbourg, Marcetta Y.
    Date: 2015-03-13
    Issue Date: 2016-01-06 11:07:00 (UTC+8)
    Publisher: American Chemical Society
    Abstract: The discovery of a diiron organometallic site in nature within the diiron hydrogenase, [FeFe]-H2ase, active site has prompted revisits of the classic organometallic chemistry involving the Fe–Fe bond and bridging ligands, particularly of the (μ-SCH2XCH2S)[Fe(CO)3]2 and (μ-SCH2XCH2S)[Fe(CO)2L]2 (X = CH2, NH; L = PMe3, CN–, and NHC’s (NHC = N-heterocyclic carbene)), derived from CO/L exchange reactions. Through the synergy of synthetic chemistry and density functional theory computations, the regioselectivity of nucleophilic (PMe3 or CN–) and electrophilic (nitrosonium, NO+) ligand substitution on the diiron dithiolate framework of the (μ-pdt)[Fe(CO)2NHC][Fe(CO)3] complex (pdt = propanedithiolate) reveals the electron density shifts in the diiron core of such complexes that mimic the [FeFe]-H2ase active site. While CO substitution by PMe3, followed by reaction with NO+, produces (μ-pdt)(μ-CO)[Fe(NHC)(NO)][Fe(CO)2PMe3]+, the alternate order of reagent addition produces the structural isomer (μ-pdt)[Fe(NHC)(NO)PMe3][Fe(CO)3]+, illustrating how the nucleophile and electrophile choose the electron-poor metal and the electron-rich metal, respectively. Theoretical explorations of simpler analogues, (μ-pdt)[Fe(CO)2CN][Fe(CO)3]−, (μ-pdt)[Fe(CO)3]2, and (μ-pdt)[Fe(CO)2NO][Fe(CO)3]+, provide an explanation for the role that the electron-rich iron moiety plays in inducing the rotation of the electron-poor iron moiety to produce a bridging CO ligand, a key factor in stabilizing the electron-rich iron moiety and for support of the rotated structure as found in the enzyme active site.
    Relation: Inorganic Chemistry 54(7), pp.3523-3535
    DOI: 10.1021/acs.inorgchem.5b00072
    Appears in Collections:[化學學系暨研究所] 期刊論文

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