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A two-step reaction scheme leading to singlet carbene species that can be detected under matrix conditions for the reaction of Zr(3F) with either CH3F or CH3CN

Authors

  • Ana E. Torres,

    1. Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Mexico, D.F.
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  • Guadalupe Castro,

    1. Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Mexico, D.F.
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  • Ricardo Pablo-Pedro,

    1. Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Mexico, D.F.
    Current affiliation:
    1.  Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts
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  • Fernando Colmenares

    Corresponding author
    1. Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Mexico, D.F.
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Abstract

The results obtained from CASSCF-MRMP2 calculations are used to rationalize the singlet complexes detected under matrix-isolation conditions for the reactions of laser-ablated Zr(3F) atoms with the CH3F and CH3CN molecules, without invoking intersystem crossings between electronic states with different multiplicities. The reaction Zr(3F) + CH3F evolves to the radical products ZrF· + ·CH3. This radical asymptote is degenerate to that emerging from the singlet channel of the reactants Zr(1D) + CH3F because they both exhibit the same electronic configuration in the metal fragment. Hence, the caged radicals obtained under cryogenic-matrix conditions can recombine through triplet and singlet paths. The recombination of the radical species along the low-multiplicity channel produces the inserted structures H3C[BOND]Zr[BOND]F and H2C[DOUBLE BOND]ZrHF experimentally detected. For the Zr(3F) + CH3CN reaction, a similar two-step reaction scheme involving the radical fragments ZrNC· + ·CH3 explains the presence of the singlet complexes H3C[BOND]Zr[BOND]NC and H2C[DOUBLE BOND]Zr(H)NC revealed in the IR-matrix spectra upon UV irradiation. © 2014 Wiley Periodicals, Inc.

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