Reactions between imines and tungsten alkylidyne complexes are studied. The trianionic pincer ligand supported alkylidyne [tBuOCO]WCC(CH3)3(THF)2 (1) reacts with N-(R)-1-phenylmethanimine (PMI-R, R = Me, Ph, Bn, and TMS) yielding [tBuOC(H)O]W(η2-tBuCCPh)N(R) (4-R), products from metathesis reaction. In contrast, the non-pincer alkylidyne (tBuO)3WCC(CH3)3 does not react with PMI-R imines.