The activated reaction of dichlorocarbene with triplet molecular oxygen

Abstract

The reaction of dichlorocarbene and molecular oxygen in their respective ground states is hindered by a considerable barrier rendering a diffusion controlled formation of the resulting Criegee intermediate unlikely.

Designing a σ0π2 singlet ground state carbene from dicationic carbones

“…Our lab has shown that this results in unusual chemistry, such as a preference for least-motion reactions with H 2 and alkenes 12 as opposed to other ordinary carbenes 13,14 as well as a swift reaction with triplet oxygen at cryogenic temperatures 15 despite the commonly encountered spin state selectivity of carbenes. 16,17…”

“…Our lab has shown that this results in unusual chemistry, such as a preference for least-motion reactions with H 2 and alkenes 12 as opposed to other ordinary carbenes 13,14 as well as a swift reaction with triplet oxygen at cryogenic temperatures 15 despite the commonly encountered spin state selectivity of carbenes. 16,17 A major breakthrough in the chemistry of s 0 p 2 carbenes has recently been accomplished with the isolation of rhodium-Fig. 1 The usually high-lying s 0 p 2 configuration of carbenes (A) becomes the ground state in 2 (B) and 4 (C) facilitating their unusual chemistry.…”