New insights into solvolysis and reorganization energy from gas-phase, electrochemical, and theoretical studies of oxo-Tp*Mo(V) molecules.

ABSTRACT: Molecules of the general form Tp*MoO(OR)(2) [where Tp* = hydrotris(3,5-dimethyl-1-pyrazolyl)borate and (OR)(2) = (OMe)(2), (OEt)(2), and (O(n)Pr)(2) for alkoxide ligands and (OR)(2) = O(CH(2))(3)O, O(CH(2))(4)O, and O[CH(CH(3))CH(2)CH(CH(3))]O for diolato ligands] were studied using gas-phase photoelectron spectroscopy, cyclic voltammetry, and density functional theory (DFT) calculations to examine the effect of increasing ligand size and structure on the oxomolybdenum core. Oxidation potentials and first ionization energies are shown to be sensitive to the character of the diolato and alkoxide ligands. A linear correlation between the solution-phase oxidation potentials and the gas-phase ionization energies resulted in an unexpected slope of greater than unity. DFT calculations indicated

SUBMITTER: Vannucci AK 

PROVIDER: S-EPMC2768231 | biostudies-literature | 2009 Sep

REPOSITORIES: biostudies-literature