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