Reaction of phenylchlorocarbene and diphenylcarbene with the carbon-chlorine bond: Kinetics and mechanisms

Article abstract of DOI:10.1021/ja00032a034

The reactions of phenylchlorocarbene (PCC) and diphenylcarbene (DPC) with carbon-chlorine bonds were investigated by laser flash photolysis techniques, product studies, and electrochemical methods. The data with both carbenes are consistent with a polar chlorine atom transfer to form radical pairs. The PCC reaction can be thought of as an inner sphere electron transfer from the carbene to the carbon-halogen bond in which there is partial carbon-halogen bond formation in the transition state. The transition state is thought to involve a crossing between closed- and open-shell singlet surfaces. The data obtained in the reaction of DPC with chlorine donors resembles the data obtained with PCC but is more difficult to interpret because the multiplicity of the state reacting with the C-Cl bond is unclear.