title: Oxygen atom transfer reactivity from a dioxo-Mo(VI) complex to tertiary phosphines: synthesis, characterization, and structure of phosphoryl intermediate complexes.
abstract: The oxygen atom transfer (OAT) reactivity of TpMoO2Cl with PMe3, PEt3, and PPhMe2 (where Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate) has been investigated. The OAT reactions proceed through a diamagnetic Mo(IV) phosphoryl intermediate complex of general formula TpMoOCl(OPR3) (OPR3 = OPMe3, OPEt3, OPPhMe2), which have been isolated and characterized by 1H and 31P NMR, UV-visible, and infrared spectroscopies and electrospray ionization mass spectrometry. Solid-state crystal structures of TpMoOCl(OPMe3) and TpMoOCl(OPPhMe2) are also reported, the oxygen-to-phosphorus distances agree with a double-bond formulation and a single bond between the metal and the phosphoryl oxygen atom. The stability of the phosphoryl intermediate complexes depends on the steric properties of the coordinated phosphine-oxides. These intermediate complexes have been converted to solvent-coordinated species, TpMoOCl(solv) (solv = acetonitrile or dmf), and the coordinated solvents exchange with the bulk solvent.
authors.affiliation: Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282, USA.
authors.forename: Victor N
authors.initials: VN
authors.lastname: Nemykin
authors.forename: Partha
authors.initials: P
authors.lastname: Basu
mesh_terms: D003461:Crystallography; D004149:Dioxoles / Q000737:chemistry*; D004355:Drug Stability; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D010087:Oxides; D010720:Phosphines / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization; D013053:Spectrophotometry
chemical_list: D004149:Dioxoles; D010087:Oxides; D010720:Phosphines; D008982:Molybdenum