Density functional theory investigation of the reactions of CH2Br–I, CH2I–Br, CH2Cl–I, and CH2I–Cl isopolyhalomethanes with ethylene
Literature Information
Dongqi Wang, David Lee Phillips, Wei-Hai Fang
We report density functional theory calculations that examine the chemical reactivity of the iso-CH2X–I and iso-CH2I–X (where X = Br or Cl) species with ethylene and their isomerization reactions. The carbenoid properties and isomerization reactions of these CH2X–Y species were compared to those found previously for the CH2X–X species (where X = I, Br or Cl). The chemical reactivity of the iso-CH2X–I and iso-CH2I–X species varies with the electronegativity of the X atom and the position of the X atom in the carbon–halogen–halogen moiety. In addition, the C–X–I or C–I–X bond angles and I–X bond lengths (which vary more than in the iso-CH2X–X species) also appear to influence the chemical reactivity of the iso-CH2X–I and iso-CH2I–X species. We briefly discuss the properties of these cyclopropanation and isomerization reactions and likely consequences for using different isopolyhalomethanes and other species as methylene transfer agents.
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