Synthesis, Structure, and Chemistry of 2-Amino-Substituted Phosphirenes

The reaction of the bulky ynamine PhCC−NiPr2 with terminal phosphinidene complexes [RP−W(CO)5] affords the corresponding phosphirenes for R = Ph and OMe and the diphosphetene for R = Me. The structure of the 1-phenyl-phosphirene shows elongated P−C(N) and CC ring bonds. The reaction of this phosphirene with dimethyl acetylenedicarboxylate gives the phosphole resulting from the insertion of the alkyne into the P−C(N) bond and the tetrafunctional arene resulting from the [2+2+2] cycloaddition of one alkyne with two phosphirenes.