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C-H Bond Oxidation by MnIV-Oxo Complexes: Hydrogen-Atom Tunneling and Multistate Reactivity.
Singh, Priya; Massie, Allyssa A; Denler, Melissa C; Lee, Yuri; Mayfield, Jaycee R; Lomax, Markell J A; Singh, Reena; Nordlander, Ebbe; Jackson, Timothy A.
Afiliación
  • Singh P; The University of Kansas, Department of Chemistry and Center for Environmentally Beneficial Catalysis, 1567 Irving Hill Road, Lawrence, Kansas 66045, United States.
  • Massie AA; The University of Kansas, Department of Chemistry and Center for Environmentally Beneficial Catalysis, 1567 Irving Hill Road, Lawrence, Kansas 66045, United States.
  • Denler MC; The University of Kansas, Department of Chemistry and Center for Environmentally Beneficial Catalysis, 1567 Irving Hill Road, Lawrence, Kansas 66045, United States.
  • Lee Y; The University of Kansas, Department of Chemistry and Center for Environmentally Beneficial Catalysis, 1567 Irving Hill Road, Lawrence, Kansas 66045, United States.
  • Mayfield JR; The University of Kansas, Department of Chemistry and Center for Environmentally Beneficial Catalysis, 1567 Irving Hill Road, Lawrence, Kansas 66045, United States.
  • Lomax MJA; The University of Kansas, Department of Chemistry and Center for Environmentally Beneficial Catalysis, 1567 Irving Hill Road, Lawrence, Kansas 66045, United States.
  • Singh R; Lund University, Chemical Physics, Department of Chemistry, P.O. Box 124, SE-221 00 Lund, Sweden.
  • Nordlander E; Lund University, Chemical Physics, Department of Chemistry, P.O. Box 124, SE-221 00 Lund, Sweden.
  • Jackson TA; The University of Kansas, Department of Chemistry and Center for Environmentally Beneficial Catalysis, 1567 Irving Hill Road, Lawrence, Kansas 66045, United States.
Inorg Chem ; 63(17): 7754-7769, 2024 Apr 29.
Article en En | MEDLINE | ID: mdl-38625043
ABSTRACT
The reactivity of six MnIV-oxo complexes in C-H bond oxidation has been examined using a combination of kinetic experiments and computational methods. Variable-temperature studies of the oxidation of 9,10-dihydroanthracene (DHA) and ethylbenzene by these MnIV-oxo complexes yielded activation parameters suitable for evaluating electronic structure computations. Complementary kinetic experiments of the oxidation of deuterated DHA provided evidence for hydrogen-atom tunneling in C-H bond oxidation for all MnIV-oxo complexes. These results are in accordance with the Bell model, where tunneling occurs near the top of the transition-state barrier. Density functional theory (DFT) and DLPNO-CCSD(T1) computations were performed for three of the six MnIV-oxo complexes to probe a previously predicted multistate reactivity model. The DFT computations predicted a thermal crossing from the 4B1 ground state to a 4E state along the C-H bond oxidation reaction coordinate. DLPNO-CCSD(T1) calculations further confirm that the 4E transition state offers a lower energy barrier, reinforcing the multistate reactivity model for these complexes. We discuss how this multistate model can be reconciled with recent computations that revealed that the kinetics of C-H bond oxidation by this set of MnIV-oxo complexes can be well-predicted on the basis of the thermodynamic driving force for these reactions.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2024 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Inorg Chem Año: 2024 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos