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J Comput Chem. 2014 Apr 30;35(11):883-90. doi: 10.1002/jcc.23564. Epub 2014 Feb 24.

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.

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Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Mexico, D.F., 04510.


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((3)F) atoms with the CH3F and CH3CN molecules, without invoking intersystem crossings between electronic states with different multiplicities. The reaction Zr((3)F) + CH3 F evolves to the radical products ZrF· + ·CH3. This radical asymptote is degenerate to that emerging from the singlet channel of the reactants Zr((1)D) + CH3 F 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-Zr-F and H2C=ZrHF experimentally detected. For the Zr((3)F) + CH3 CN reaction, a similar two-step reaction scheme involving the radical fragments ZrNC· + ·CH3 explains the presence of the singlet complexes H C-Zr-NC and H2 C=Zr(H)NC revealed in the IR-matrix spectra upon UV irradiation.


carbene; intersystem-crossings; radical-recombination; transition-metals; trapped-radicals

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