Organo-aluminum,zinc and magnesium derivatives of the imidotris(amido)phosphate Me3SiNP(NHtBu)3

Reactions of (^tBuHN)₃PNSiMe₃ (1) with the alkyl-metal reagents dimethylzinc, trimethylaluminum and di-n-butylmagnesium yield the monodeprotonated complexes MeZn{(N^tBu)(NSiMe₃)P(NH^tBu)₂}] (2), Me₂Al{(N^tBu)(NSiMe₃)P(NH^tBu)₂}] (3) and Mg{(N^tBu)(NSiMe₃)P(NH^tBu)₂}₂] (4), respectively. Attempts to further deprotonate complex 2 with n-butyllithium or di-n-butylmagnesium result in nucleophilic displacement of the methylzinc fragment by lithium or magnesium. The two remaining amino protons of 3 are removed by reaction with di-n-butylmagnesium to give a heterobimetallic complex in which the coordination sphere of magnesium is completed by two molecules of THF (5 · 2THF) or one molecule of TMEDA (5 · TMEDA). Reaction of complex 3 with 1 equiv. of n-butyllithium followed by treatment of the product with di-n-butylmagnesium yields the complex {Me₂Al(N^tBu)(NSiMe₃)P(N^tBu)₂]MgBu} Li · 4THF (6 · 4THF), the first example of a triply deprotonated complex of 1 containing three different metals. Reaction of complex 5 with iodine results in cleavage of an Al–Me group to give {MeIAl(N^tBu)(NSiMe₃)P(N^tBu)₂Mg]} (7). Complexes 5 · 2THF, 5 · TMEDA, 6 · 4THF and 7 have been characterized in solution by multinuclear (¹H, ¹³C, ³¹P and ⁷Li) NMR spectroscopy, while the solid-state structures of 2, 4 and 5 · 2THF have been determined by X-ray crystallography.