C-H Functionalisation Through Singlet Chlorocarbenes Insertions – MP2 and DFT Investigations

Abstract

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 σ approach the barrier heights have been found to be ca. 2 to 5 times that of the normal σ approach.

Carbenes and Nitrenes

“…85 Computational studies were also carried out for the insertion of singlet chloro-and dichloro-carbene in the C-H bond of methane and ethane. 86 Reaction of :CH 2 with hydroxamic and thiohydroxamic acid was examined by quantum chemical …”