3 years ago

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

Multiple Mechanisms for the Thermal Decomposition of Metallaisoxazolin-5-ones from Computational Investigations
K. N. Houk, Chen-Chen Zhou, Gonzalo Jiménez-Osés, M. Frederick Hawthorne
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.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b01169

DOI: 10.1021/acs.joc.7b01169

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