New Access to and Reactions of P ‐Functional Acylphosphane Complexes

P ‐Functional (acylphosphane)tungsten complexes 4a – f have been prepared in good yields by the reaction of phosphinidenoid complexes 2a – d with acyl chlorides 3a , b . The reactions of acyl(chloro)phosphane complex 4a at –80 °C with organolithium reagents selectively led to the formation of lithiated phospha‐enolate complex 5b . The ambident reactivity of this compound was demonstrated in reactions with electrophiles such as PhC(O)Cl, MeI, and Me 3 SiCl, which yielded O ‐substituted complexes 6a , b and 8a , b and P ‐substituted complex 7 .