3H-Phosphaallenes Revisited: Facile Synthesis by Hydroalumination of Alkynylphosphines and β-Elimination, Stability and Trapping of Transient Species by Coordination to Transition Metal Atoms

Abstract

A facile method for the efficient synthesis of 3H-phosphaallenes, R-P=C=C(H)-R', is presented, which comprises treatment of dialkynylphosphines with dialkylaluminium hydrides (hydroalumination) and elimination of aluminium alkynides from intermediate alkenyl-alkynylphosphines. The stability of the phosphaallenes depends on steric shielding by the substituents at phosphorus (aryl or CH(SiMe₃ )₂ groups). Only supermesityl compounds are persistent at room temperature in solution. This simple method starting with easily accessible dialkynylphosphines and commercially available aluminium hydrides (HAlEt₂ , HAliBu₂ ) allows the generation of transient species, which were trapped by coordination to transition metals. The η¹ -coordination via a P-W bond was observed for tungsten, while the side-on coordination via the P=C bond resulted with platinum. Decomposition of the mesityl derivative yielded an unprecedented product, which may be formed by 1,3-H shift to the P atom, hydrophosphination of the P=C bond of a second phosphaallene and formation of a P-P bond.

Keywords: alkynylphosphines; coordination compounds; frustrated Lewis pairs; hydroalumination; phosphaallenes.