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

Abstract

In this study, we report a group of alkali metal aluminates bearing bis(organoamido)phosphane ligand. The starting complex {[PhP(NtBu)₂]AlMe₂}Li·OEt₂ (1) was prepared by stepwise deprotonation of the parent PhP(NHtBu)₂ by nBuLi and AlMe₃. Further derivatization of aluminate 1 was performed by the virtual substitution of lithium -{[PhP(NtBu)₂]AlMe₂}K (2), methyl substituents – {[PhP(NtBu)₂]AlH₂}Li·THF (3), modification of steric bulk and induction effects on the phosphorus atom – {[tBuP(N-2,6-iPr₂C₆H₃)₂]AlMe₂}Li·(OEt₂)₂ (4), and phosphorus atom oxidation state {[Ph(Y)P(NtBu)₂]AlMe₂}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.