Multiple Mechanisms for the Thermal Decomposition of Metallaisoxazolin-5-ones from Computational Investigations

  1. Zhou, C.-C. 2
  2. Hawthorne, M.F. 3
  3. Houk, K.N. 2
  4. Jiménez-Osés, G. 1
  1. 1 Universidad de La Rioja
    info

    Universidad de La Rioja

    Logroño, España

    ROR https://ror.org/0553yr311

  2. 2 University of California Los Angeles
    info

    University of California Los Angeles

    Los Ángeles, Estados Unidos

    ROR https://ror.org/046rm7j60

  3. 3 University of Missouri
    info

    University of Missouri

    Columbia, Estados Unidos

    ROR https://ror.org/02ymw8z06

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Revista:
Journal of Organic Chemistry

ISSN: 0022-3263

Año de publicación: 2017

Volumen: 82

Número: 16

Páginas: 8438-8443

Tipo: Artículo

DOI: 10.1021/ACS.JOC.7B01169 SCOPUS: 2-s2.0-85027544625 WoS: WOS:000408285500010 GOOGLE SCHOLAR

Otras publicaciones en: Journal of Organic Chemistry

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Resumen

The thermal decompositions of metallaisoxazolin-5-ones containing Ir, Rh, or Co are investigated using density functional theory. The experimentally observed decarboxylations of these molecules are found to proceed through retro-(3+2)-cycloaddition reactions, generating the experimentally reported η2 side-bonded nitrile complexes. These intermediates can isomerize in situ to yield a η1 nitrile complex. A competitive alternative pathway is also found where the decarboxylation happens concertedly with an aryl migration process, producing a η1 isonitrile complex. Despite their comparable stability, these η1 bonded species were not detected experimentally. The experimentally detected η2 side bound species are likely involved in the subsequent C-H activation reactions with hydrocarbon solvents reported for some of these metallaisoxazolin-5-ones. © 2017 American Chemical Society.