A density functional theory study of the reactions of dichlorocarbene and isodichloromethane with H2O

A density functional theory investigation of the reactions of dichlorocarbene and isodichlorocarbene with H2O is reported. The reactions are found to be noticeably different for dichlorocarbene and isodichloromethane and can be attributed to their different structures and properties. The isodichloromethane species can react with H2O by both direct and indirect O-H insertion reactions with the indirect reaction having a much lower barrier to reaction than the direct reaction. However, the dichlorocarbene reacts with H2O predominantly via a direct OH insertion reaction that has a barrier to reaction noticeably lower than both of the isodichloromethane reactions.