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Baron Peters Susannah Scott S. Michael Stewart

Baron Peters Susannah Scott S. Michael Stewart. Mechanistic studies of peroxide activation by methyltrioxorhenium. Gibbs free energy for mechanism in literature. more accurate results for equilibria from mPW1PW91 than from B3LYP. triple- x and 2f-polarized basis with

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Baron Peters Susannah Scott S. Michael Stewart

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  1. Baron Peters Susannah Scott S. Michael Stewart Mechanistic studies of peroxide activation by methyltrioxorhenium Gibbs free energy for mechanism in literature • more accurate results for equilibria • from mPW1PW91 than from B3LYP. • triple-x and 2f-polarized basis with • ECP needed for Re atom • previous mechanisms and calculations • for MTO+H2O2 reactions give DH‡ too • large and DS‡ too small [Gonzales et al., • J. Am. Chem. Soc. 129, 15794 (2007)] • water-assisted mechanism matches • expt; also explains rapid 18O exchange • activation parameters with CPCM • solvent and tunneling correction • derived HOO- concentration in water with • MTO and Lewis base like pyridine; also • derived HOO- catalyzed rate expression Gibbs free energy for water assisted mechanism B Peters, SM Stewart, and SL Scott, in preparation

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