C-H functionalisation through singlet chlorocarbenes insertions - MP2 and DFT investigations

Abstract

The insertion reactions of singlet mono and dichlorocarbenes ( 1 CHCl and 1 CCl 2 into primary, secondary and tertiary C-H bonds of methane, ethane, propane, n-butane and iso-butane have been investigated at ab initio (MP2) and DFT levels invoking 6-31g(d, p) basis set. Among the σ and π insertions into the said alkane C-H, both MP2 and DFT predict that the σ approach is slightly favoured over the π approach. For inverted o approach the barrier heights have been found to be ca. 2 to 5 times that of the normal σ approach. © Springer-Verlag Berlin Heidelberg 2006.