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• W2331166205 endingPage "13917" @default.
• W2331166205 startingPage "13904" @default.
• W2331166205 abstract "The formation of peroxorhenium complexes by activation of H2O2 is key in selective oxidation reactions catalyzed by CH3ReO3 (methyltrioxorhenium, MTO). Previous reports on the thermodynamics and kinetics of these reactions are inconsistent with each other and sometimes internally inconsistent. New experiments and calculations using density functional theory with the ωB97X-D and augmented def2-TZVP basis sets were conducted to better understand these reactions and to provide a strong experimental foundation for benchmarking computational studies involving MTO and its derivatives. Including solvation contributions to the free energies as well as tunneling corrections, we compute negative reaction enthalpies for each reaction and correctly predict the hydration state of all complexes in aqueous CH3CN. New rate constants for each of the forward and reverse reactions were both measured and computed as a function of temperature, providing a complete set of consistent activation parameters. New, independent measurements of equilibrium constants do not indicate strong cooperativity in peroxide ligand binding, as was previously reported. The free energy barriers for formation of both CH3ReO2(η(2)-O2) (A) and CH3ReO(η(2)-O2)2(H2O) (B) are predominantly entropic, and the former is much smaller than a previously reported value. Computed rate constants for a direct ligand-exchange mechanism, and for a mechanism in which a water molecule facilitates ligand-exchange via proton transfer in the transition state, differ by at least 7 orders of magnitude. The latter, water-assisted mechanism is predicted to be much faster and is consequently in much closer agreement with the experimentally measured kinetics. Experiments confirm the predicted catalytic role of water: the kinetics of both steps are strongly dependent on the water concentration, and water appears directly in the rate law." @default.
• W2331166205 created "2016-06-24" @default.
• W2331166205 creator A5003451698 @default.
• W2331166205 creator A5026770434 @default.
• W2331166205 creator A5029871622 @default.
• W2331166205 creator A5043597178 @default.
• W2331166205 date "2013-11-21" @default.
• W2331166205 modified "2023-09-23" @default.
• W2331166205 title "Water-Catalyzed Activation of H₂O₂ by Methyltrioxorhenium: A Combined Computational–Experimental Study" @default.
• W2331166205 cites W1564397078 @default.
• W2331166205 cites W1963823055 @default.
• W2331166205 cites W1966182479 @default.
• W2331166205 cites W1966233576 @default.
• W2331166205 cites W1966365303 @default.
• W2331166205 cites W1966389515 @default.
• W2331166205 cites W1970463434 @default.
• W2331166205 cites W1971209681 @default.
• W2331166205 cites W1971241275 @default.
• W2331166205 cites W1975851499 @default.
• W2331166205 cites W1986391889 @default.
• W2331166205 cites W1987262911 @default.
• W2331166205 cites W1988165294 @default.
• W2331166205 cites W1988475924 @default.
• W2331166205 cites W1988675445 @default.
• W2331166205 cites W1989021710 @default.
• W2331166205 cites W1989620878 @default.
• W2331166205 cites W1989973269 @default.
• W2331166205 cites W1990280848 @default.
• W2331166205 cites W1994080636 @default.
• W2331166205 cites W1996846370 @default.
• W2331166205 cites W1997151511 @default.
• W2331166205 cites W1997551594 @default.
• W2331166205 cites W1998106856 @default.
• W2331166205 cites W1998228085 @default.
• W2331166205 cites W2001811780 @default.
• W2331166205 cites W2003271076 @default.
• W2331166205 cites W2004486832 @default.
• W2331166205 cites W2007663400 @default.
• W2331166205 cites W2009704081 @default.
• W2331166205 cites W2010111918 @default.
• W2331166205 cites W2015723183 @default.
• W2331166205 cites W2016059430 @default.
• W2331166205 cites W2017041202 @default.
• W2331166205 cites W2017572700 @default.
• W2331166205 cites W2021175659 @default.
• W2331166205 cites W2021231925 @default.
• W2331166205 cites W2022272063 @default.
• W2331166205 cites W2023279035 @default.
• W2331166205 cites W2026041973 @default.
• W2331166205 cites W2027240263 @default.
• W2331166205 cites W2027386489 @default.
• W2331166205 cites W2027599336 @default.
• W2331166205 cites W2027769799 @default.
• W2331166205 cites W2028929023 @default.
• W2331166205 cites W2032481383 @default.
• W2331166205 cites W2032718131 @default.
• W2331166205 cites W2032897498 @default.
• W2331166205 cites W2036618001 @default.
• W2331166205 cites W2039559098 @default.
• W2331166205 cites W2040591591 @default.
• W2331166205 cites W2044490585 @default.
• W2331166205 cites W2048872604 @default.
• W2331166205 cites W2049851944 @default.
• W2331166205 cites W2052705653 @default.
• W2331166205 cites W2053269751 @default.
• W2331166205 cites W2053871846 @default.
• W2331166205 cites W2054230964 @default.
• W2331166205 cites W2056238197 @default.
• W2331166205 cites W2057041338 @default.
• W2331166205 cites W2057980421 @default.
• W2331166205 cites W2058848030 @default.
• W2331166205 cites W2061788527 @default.
• W2331166205 cites W2062991523 @default.
• W2331166205 cites W2063415723 @default.
• W2331166205 cites W2066530207 @default.
• W2331166205 cites W2068077887 @default.
• W2331166205 cites W2068302876 @default.
• W2331166205 cites W2068617439 @default.
• W2331166205 cites W2069306399 @default.
• W2331166205 cites W2071990116 @default.
• W2331166205 cites W2072796268 @default.
• W2331166205 cites W2073189783 @default.
• W2331166205 cites W2073328513 @default.
• W2331166205 cites W2074386447 @default.
• W2331166205 cites W2078608340 @default.
• W2331166205 cites W2079282984 @default.
• W2331166205 cites W2081159460 @default.
• W2331166205 cites W2082903593 @default.
• W2331166205 cites W2086262548 @default.
• W2331166205 cites W2086648086 @default.
• W2331166205 cites W2089545684 @default.
• W2331166205 cites W2090725483 @default.
• W2331166205 cites W2091037892 @default.
• W2331166205 cites W2091955106 @default.
• W2331166205 cites W2092578986 @default.
• W2331166205 cites W2093567155 @default.
• W2331166205 cites W2096517067 @default.
• W2331166205 cites W2105363562 @default.

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