Generation and Trapping of Terminal Phosphinidene Complex [CF3P‐W(CO)5

Abstract

AbstractThe LUMO of [CF3P−W(CO)5] is lower in energy than the LUMO of [ClP−W(CO)5] by 0.30 eV and [CF3P−W(CO)5] is the most electrophilic phosphinidene tungstenpentacarbonyl complex described so far. It is generated by reaction of dimethyl acetylenedicarboxylate with the appropriate 1‐trifluoromethylphosphole complex at 80 oC in toluene. It reacts normally with alkynes to give 1‐trifluoromethylphosphirene complexes. The reaction with alkenes works only with electron‐rich species. The phosphirane complexes appear to be unstable when electron‐poor C=C double bonds are used such as with trans‐stilbene. This highlights the importance of the P to C=C backbonding in the stability of the phosphirane adducts.