title: Reduced thione ligation is preferred over neutral phosphine ligation in diiron biomimics regarding electronic functionality: a spectroscopic and computational investigation.
abstract: Sulfur containing ligands with a thiolate-thiyl radical character are much superior than phosphine ligands in the active site modeling of [FeFe]hydrogenase regarding electronic functionality on charge communication and modulation of the electronic structure of the catalytic metal center.
authors.affiliation: Institute of Chemistry, Academia Sinica, Nankang, Taipei 115, Taiwan. mhchiang@chem.sinica.edu.tw and Molecular Science Technology Program, TIGP, Institute of Chemistry, Academia Sinica, Nankang, Taipei 115, Taiwan and Department of Chemistry, National Tsing Hua University, Hsinchu 300, Taiwan.
authors.forename: Tao-Hung
authors.initials: TH
authors.lastname: Yen
authors.affiliation: Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, Taipei 106, Taiwan.
authors.forename: Zong-Cheng
authors.initials: ZC
authors.lastname: He
authors.affiliation: Instrumentation Center, National Taiwan University, Taipei 106, Taiwan.
authors.forename: Gene-Hsiang
authors.initials: GH
authors.lastname: Lee
authors.affiliation: Institute of Chemistry, Academia Sinica, Nankang, Taipei 115, Taiwan. mhchiang@chem.sinica.edu.tw.
authors.forename: Mei-Chun
authors.initials: MC
authors.lastname: Tseng
authors.affiliation: Department of Chemistry, National Taiwan University, Taipei 106, Taiwan.
authors.forename: Yu-Hsuan
authors.initials: YH
authors.lastname: Shen
authors.affiliation: Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, Taipei 106, Taiwan.
authors.forename: Tien-Wen
authors.initials: TW
authors.lastname: Tseng
authors.affiliation: Department of Chemistry, National Tsing Hua University, Hsinchu 300, Taiwan.
authors.forename: Wen-Feng
authors.initials: WF
authors.lastname: Liaw
authors.affiliation: Institute of Chemistry, Academia Sinica, Nankang, Taipei 115, Taiwan. mhchiang@chem.sinica.edu.tw and Molecular Science Technology Program, TIGP, Institute of Chemistry, Academia Sinica, Nankang, Taipei 115, Taiwan.
authors.forename: Ming-Hsi
authors.initials: MH
authors.lastname: Chiang
mesh_terms: D020134:Catalytic Domain; D055664:Electrochemical Techniques; D006864:Hydrogenase / Q000737:chemistry* / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000737:chemistry* / Q000378:metabolism; D008024:Ligands; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010720:Phosphines / Q000737:chemistry* / Q000378:metabolism; D011789:Quantum Theory; D017550:Spectroscopy, Fourier Transform Infrared; D013871:Thiones / Q000737:chemistry* / Q000378:metabolism
chemical_list: D007506:Iron-Sulfur Proteins; D008024:Ligands; D010720:Phosphines; D013871:Thiones; C118830:iron hydrogenase; D006864:Hydrogenase; C044646:phosphine