Ab initio self-consistent field calculations of lithium atom insertion into a carbon-hydrogen bond of methane

John G. McCaffrey, Raymond A. Poirier, Geoffrey A. Ozin, Imre G. Csizmadia

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8 Citations (Scopus)

Abstract

The energy and geometries of the lowest 2A1 and 2E states of the product resulting from lithium atom insertion into a C-H bond of methane in C3v symmetry were obtained by ab initio molecular orbital calculations. Geometries were optimized with three different basis sets, STO-3G, 3-21G, and 6-31G**. The possible pathways to insertion of the lithium atom into a CH bond of methane were also considered. The geometry of the more stable 2A1 state suggested that the inserted molecule is best described as a methyl radical interacting with lithium hydride, where the C-Li bond can be taken as a single electron bond. The 2E state showed a different behavior in that a stronger interaction exists between the methyl and lithium hydride, with the C-Li bond considerably shorter and correspondingly longer C-H bonds. In this case the C-Li bond can be considered as a two-electron bond. The barrier for the formation of methyllithium hydride appears to be associated with the abstraction of the hydride. A brief comparison of the bonding in CH3CuH with that in CH3LiH showed considerable similarities.

Original languageEnglish
Pages (from-to)2898-2902
Number of pages5
JournalJournal of physical chemistry
Volume88
Issue number13
DOIs
Publication statusPublished - Jan 1 1984

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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