Fragmentation of White Phosphorus by a Cyclic (Alkyl)(Amino)Alumanyl Anion

The stable cyclic (alkyl)­(amino)­alumanyl anion (CAAAl) 3 reacts with white phosphorus (P4) under ambient conditions, in which P4 is fragmented into a P1 unit to afford the bis­(alumanyl)­phosphide 2, demonstrating the direct formation of a P anion from an Al anion. Structural and electronic features of the latter were fully characterized by standard spectroscopic means, X-ray diffraction analysis, and computational studies, which revealed that 2 bears highly polarized Al (δ+) and P (δ−) and relatively short Al–P bonds, indicative of the σ-donating and π-accepting nature of CAAAl groups.