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(N t Bu) 2 ]AlMe 2 }Li·OEt 2 (1) was prepared by stepwise deprotonation of the parent PhP(NH t Bu) 2 by n BuLi and AlMe 3 . Further derivatization of aluminate 1 was performed by the virtual substitution of lithium -{[PhP(N t Bu) 2 ]AlMe 2 }K (2), methyl substituents - {[PhP(N t Bu) 2 ]AlH 2 }Li·THF (3), modification of steric bulk and induction effects on the phosphorus atom - {[ t BuP( N -2,6-iPr 2 C 6 H 3 ) 2 ]AlMe 2 }Li·(OEt 2 ) 2 (4), and phosphorus atom oxidation state {[Ph(Y)P(N t Bu) 2 ]AlMe 2 }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 via the formation of P-E bond (E = Si, Ge, Sn, Pb, P, and C) and followed by P(III) → P(V) tautomeric shift.