Rearrangement of bis(alkylidynyl)phosphines to phosphaacyls

Abstract

A range of bis(alkylidynyl)phosphines RP{CRM(CO)2(Tp*)}2 (M =Mo, W; R = Cl, Ph, Cy; Tp* = hydrotris(dimethylpyrazolyl)borate) are obtained from the reactions of [M(RCLi)(CO)2(Tp*)] with Cl2PR or alternatively via the palladium(0)-mediated reactions of [W(RCBr)(CO)2(Tp*)] with RPH2 (R = Py, Cy). The complexes RP{CRW(CO)2(Tp*)}2 rearrange slowly (R = Cl) or on heating (R = Ph) to afford the isomeric phosphaacyls [W2(l:g1-C;g2-C,P-CCPR)(CO)4(Tp*)2].