Synthesis and reactivity of alkali metal aluminates bearing bis(organoamido)phosphane ligand.

In this study, we report a group of alkali metal aluminates bearing bis(organoamido)phosphane ligand. The starting complex {[PhP(NBu)]AlMe}Li·OEt (1) was prepared by stepwise deprotonation of the parent PhP(NHBu) by BuLi and AlMe. Further derivatization of aluminate 1 was performed by the virtual substitution of lithium -{[PhP(NBu)]AlMe}K (2), methyl substituents - {[PhP(NBu)]AlH}Li·THF (3), modification of steric bulk and induction effects on the phosphorus atom - {[BuP(-2,6-iPrCH)]AlMe}Li·(OEt) (4), and phosphorus atom oxidation state {[Ph(Y)P(NBu)]AlMe}Li (Y = O (5), S (6), Se (7), Te (8)). The structure causing non-covalent interactions in 1-4 were evaluated with the help of theoretical calculations and topological analysis ranging from π-electron system-metal to agostic interactions of various types. The further reactions of 1 with various nucleophiles were found to be a versatile tool for the preparation of iminophosphonamides the formation of P-E bond (E = Si, Ge, Sn, Pb, P, and C) and followed by P(III) → P(V) tautomeric shift.