Reactions of Dichlorocarbene with Phosphorus Compounds in Low Coordination(Low-.SIGMA.) States.

Reactions of low coordinated phosphorus compounds with dichlorocarbene and successive conversions of the resulting phosphiranes to phosphacumulenes are reviewed. Sterically protected diphosphenes reacted with dichlorocarbene to give the corresponding dichlorodiphosphiranes , which reacted with methyllithium to give 1,3-diphosphaallenes. Similarly , the reaction of (E )-or ( Z)-2-phenyl-1-(2 ,4 ,6-tri-t-butylphenyl)-1-phosphaethenes with dichlorocarbene afforded trans-phosphirane , which was converted to 1-phosphaallene. In some cases , the reactions of dichlorocarbene with 1-phosphaallenes , 1, 3-diphosphaallenes , or 1-phosphabutatrienes resulted in the formation of the rearranged products . Reactions of dichlorocarbene with other phosphorus species in low coordination states such as 1-aza-3-phosphaallene, 1,4-diphosphabutatriene , or phosphaalkyne are also described.