title: 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.
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((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.
authors.affiliation: Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Mexico, D.F., 04510.
authors.forename: Ana E
authors.initials: AE
authors.lastname: Torres
authors.forename: Guadalupe
authors.initials: G
authors.lastname: Castro
authors.forename: Ricardo
authors.initials: R
authors.lastname: Pablo-Pedro
authors.forename: Fernando
authors.initials: F
authors.lastname: Colmenares
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D054879:Halogenation; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D013816:Thermodynamics; D015040:Zirconium / Q000737:chemistry*
chemical_list: D000097:Acetonitriles; D005609:Free Radicals; D006845:Hydrocarbons, Fluorinated; C030011:carbene; C029999:fluoromethane; D015040:Zirconium; D008697:Methane; C032159:acetonitrile
keywords: carbene; intersystem-crossings; radical-recombination; transition-metals; trapped-radicals