title: Electronic structure of bent titanocene complexes with chelated dithiolate ligands.
abstract: Gas-phase photoelectron spectroscopy and density functional theory have been utilized to investigate the interactions between the p orbitals of dithiolate ligands and d orbitals of titanium in bent titanocene complexes as minimum molecular models of active site features of pyranopterin Mo/W enzymes. The compounds Cp(2)Ti(S-S) [where (S-S) is 1,2-ethenedithiolate (S(2)C(2)H(2)), 1, 1,2-benzenedithiolate (bdt), 2, or 1,3-propanedithiolate (pdt), 3, and Cp(-) is cyclopentadienyl] provide access to a formal 16-electron d(0) electronic configuration at the metal. A "dithiolate-folding-effect" involving an interaction of metal and sulfur orbitals is demonstrated in complexes with arene- and enedithiolates. This effect is not observed for the alkanedithiolate in complex 3.
authors.affiliation: Department of Chemistry, The University of Arizona, Tucson, Arizona 85721, USA.
authors.forename: J Jon A
authors.initials: JJ
authors.lastname: Cooney
authors.forename: Matthew A
authors.initials: MA
authors.lastname: Cranswick
authors.forename: Nadine E
authors.initials: NE
authors.lastname: Gruhn
authors.forename: Hemant K
authors.initials: HK
authors.lastname: Joshi
authors.forename: John H
authors.initials: JH
authors.lastname: Enemark
mesh_terms: D001665:Binding Sites; D004563:Electrochemistry; D007700:Kinetics; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry* / Q000378:metabolism; D009942:Organometallic Compounds / Q000737:chemistry* / Q000378:metabolism; D050862:Oxidoreductases Acting on Sulfur Group Donors / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry* / Q000378:metabolism
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; C406884:titanocene; D008982:Molybdenum; D050862:Oxidoreductases Acting on Sulfur Group Donors