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Quantitation of the ligand effect in oxo-transfer reactions of dioxo-Mo(VI) trispyrazolyl borate complexes.


ABSTRACT: The oxygen atom transfer reactivity (OAT) of dioxo-Mo(VI) complexes of hydrotrispyrazolyl borate (hydrotris(3,5-dimethylpyrazolyl)borate, Tp(Me2); hydrotris(3-isopropylpyrazol-1-yl)borate, Tp(iPr)) with tertiary phosphines (PMe(3), PMe(2)Ph, PEt(3), PEt(2)Ph, PBu(n)(3), PMePh(2), or PEtPh(2)) has been investigated. In acetonitrile, these reactions proceed via the formation of a phosphoryl intermediate complex that undergoes a solvolysis reaction. We report the synthesis and characterization of several phosphoryl complexes. The rates of formation of phosphoryl complexes and their solvation were determined by spectrophotometry. The rates of the reactions and the properties of the phosphoryl species were investigated using the Quantitative Analysis of Ligand Effect (QALE) methodology. The res

SUBMITTER: Basu P 

PROVIDER: S-EPMC3566299 | biostudies-literature | 2013 Mar

REPOSITORIES: biostudies-literature