title: Synthesis, characterization, and biomimetic chemistry of cis-oxosulfidomolybdenum(VI) complexes stabilized by an intramolecular Mo(O)=S...S interaction.
abstract: The reactions of jade-green Tp*MoIVO(S2PR2) [Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate; R = Et, Pri, Ph] with propylene sulfide produce ochre-red Tp*MoVIOS{SP(S)R2}. The complexes have been characterized by microanalysis, mass spectrometry, cyclic voltammetry, spectroscopy (IR, NMR, UV-vis, and X-ray absorption), and X-ray crystallography. The distorted-octahedral isopropyl and phenyl derivatives feature a tridentate fac-Tp* ligand, a terminal oxo ligand, and a unique five-membered Mo(=S){SP(=S)R2 ring moiety formed by a weak, intramolecular, bonding interaction between the Mo=S1 and (uncoordinated) S3=P moieties. The Mo=S1 [2.227(2) A (R = Pri) and 2.200(2) A (R = Ph)] and S1...S3 distances [2.396(3) A (R = Pri) and 2.383(2) A (R = Ph)] are indicative of a pi-bonded Mo=S1 unit and a weak (bond order ca. 1/3) S1...S3 interaction; the solid-state structures are maintained in solution according to S K-edge X-ray absorption data. The complexes react with excess cyanide to form thiocyanate and Tp*MoO(S2PR2), under anaerobic conditions, or Tp*MoO2(S2PR2), under aerobic conditions; the latter models the production of thiocyanate and desulfo molybdenum hydroxylases upon cyanolysis of molybdenum hydroxylases. The complexes react with triphenylphosphine to give Tp*MoO(S2PR2) and SPPh3, with cobaltocene or hydrosulfide ion to produce [Tp*MoVOS(S2PR2)]-, and with ferrocenium salts to yield [Tp*MoVO(S3PR2)]+; in the last two reactions, Mo(V) is produced by direct or induced internal redox reactions, respectively. The presence of the Mo(O)=S...S interaction does not radically lengthen the Mo=S bond in the complexes or preclude them from reactions typical of unperturbed oxosulfidomolybdenum(VI) complexes.
authors.affiliation: School of Chemistry, University of Melbourne, Victoria 3010, Australia.
authors.forename: Les J
authors.initials: LJ
authors.lastname: Laughlin
authors.forename: Aston A
authors.initials: AA
authors.lastname: Eagle
authors.forename: Graham N
authors.initials: GN
authors.lastname: George
authors.forename: Edward R T
authors.initials: ER
authors.lastname: Tiekink
authors.forename: Charles G
authors.initials: CG
authors.lastname: Young
mesh_terms: D040761:Biomimetic Materials / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D004583:Electrons; D008024:Ligands; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D013057:Spectrum Analysis; D013455:Sulfur / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D013455:Sulfur; D008982:Molybdenum