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. Issue 11 (24th February 2014)

• Record Type: Journal Article
• Authors: Torres, Ana E.; Castro, Guadalupe; Pablo‐Pedro, Ricardo; Colmenares, Fernando
• Is Part Of: Journal of computational chemistry. Volume 35:Issue 11(2014)
• Page Start: 883
• Page End: 890
• Publication Date: 2014-02-24
• Subjects: Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.23564
• Languages: English
• ISSNs: 0192-8651

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>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ZrF and H₂C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ZrNC and H₂CZr(H)NC revealed in the IR‐matrix spectra upon UV irradiation. © 2014 Wiley Periodicals, Inc.</p> </abstract>