title: New oxovanadium bis(1,2-dithiolate) compounds that mimic the hydrogen-bonding interactions at the active sites of mononuclear molybdenum enzymes.
abstract: Reaction of VO(acac)(2) with 1,2-dithiols in the presence of triethylamine gives pentacoordinate oxovanadium complexes [HNEt(3)](2)[VO(bdt)(2)] (1), [HNEt(3)](2)[VO(tdt)(2)] (2), and [HNEt(3)](2)[VO(bdtCl(2))(2)] (3) (where H(2)bdt = 1,2-benzenedithiol, H(2)tdt = 3,4-toluenedithiol, and H(2)bdtCl(2) = 3,6-dichloro-1,2-benzenedithiol). Compounds 1-3 have been characterized by IR, UV/visible, EPR, and mass spectroscopies. The X-ray crystal stuctures of 1 and 2 show hydrogen-bonding interactions between the terminal oxo atom and triethylammonium counterions and between ligand sulfur atoms and the counterions. These interactions are comparable with those found at the active sites of mononuclear molybdenum enzymes.
authors.affiliation: Department of Chemistry, University of Arizona, Tucson 85721-0041, USA.
authors.forename: J Jon A
authors.initials: JJ
authors.lastname: Cooney
authors.forename: Michael D
authors.initials: MD
authors.lastname: Carducci
authors.forename: Anne E
authors.initials: AE
authors.lastname: McElhaney
authors.forename: Hugh D
authors.initials: HD
authors.lastname: Selby
authors.forename: John H
authors.initials: JH
authors.lastname: Enemark
mesh_terms: D001665:Binding Sites; D018360:Crystallography, X-Ray; D003901:Desulfovibrio / Q000201:enzymology; D004578:Electron Spin Resonance Spectroscopy; D006860:Hydrogen Bonding; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D018716:Molecular Mimicry; D008982:Molybdenum / Q000737:chemistry*; D009565:Nitrate Reductases / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D017968:Vanadium Compounds / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D017968:Vanadium Compounds; D008982:Molybdenum; D009565:Nitrate Reductases