K. Krogh-jespersen et al., Ab initio electronic structure calculations on chlorocarbene-ethylene and chlorocarbene-benzene complexes, J AM CHEM S, 121(26), 1999, pp. 6269-6274
Interaction energies for carbene-solvent complex formation have been comput
ed at the MP2/6-311+G**//MP2/6-31G* level, including full counterpoise corr
ections. Our results indicate that chlorocarbenes do not form stable comple
xes with ethylene at ambient temperatures and react with tetramethylethylen
e to form cyclopropanes without an activation energy barrier. Chlorocarbene
s and benzene form weakly interacting but thermally stable 1:1 and 1:2 pi-t
ype complexes. Two pi-type complexes and a hydrogen-bonded ylidic structure
were obtained for the 1:1 methylchlorocarbene-anisole system. The formatio
n of carbene-solvent complexes might modulate carbenic reactivity in aromat
ic solvents.