First Cyclic Carbodiphosphoranes of Copper(I) and Gold(I) and Their Application in the Catalytic Cleavage of X−H Bonds (X = N and O)

Three new carbodiphosphorane complexes, (PHCP)M(tBuO) (PHCP = carbodiphosphorane; M = Cu, Au) and (PHCP)CuCl, were readily prepared by reaction of the carbodiphosphorane 2 with CuCl or AuCl(Me2S). The three complexes have been fully characterized, and their crystal structures have been determined. The two tert-butoxide complexes were tested in the catalytic anti-Markovnikov hydroamination and hydroalkoxylation of acrylonitrile, involving the first catalytic application of a carbodiphosphorane complex reported to date.