Syntheses and Structures of P-Anilino-P-chalcogeno- and P-Anilino-P-iminodiazasilaphosphetidines and Their Group 12 and 13 Metal Compounds

The P-anilino-P-chalcogeno(imino)diazasilaphosphetidines [Me₂Si(μ-N^tBu)₂PE(NHPh)] (E = O (3), S (4), Se (5), N-p-tolyl (6)) were synthesized by oxidizing the P-anilinodiazasilaphosphetidine [Me₂Si(N^tBu)₂P(NHPh)] (2) with cumene hydroperoxide, sulfur, selenium, and p-tolyl azide, respectively. The lithium salt of 4 reacted with thallium monochloride to produce {[Me₂Si(μ-N^tBu)₂PS(NPh)-κN-κS]Tl} (7), which features a two-coordinate thallium atom. Treatment of 4−6 with AlMe₃ gave the monoligand dimethylaluminum complexes {[Me₂Si(μ-N^tBu)₂PE(NPh)-κN-κE]AlMe₂} (E = S (8), Se (9), N-p-tolyl (10)), respectively. In these complexes the aluminum atom is tetrahedrally coordinated by one chelating ligand and two methyl groups, as a single-crystal X-ray analysis of 8 showed. A 2 equiv amount of 4−6 reacted with diethylzinc to produce the homoleptic diligand complexes {[Me₂Si(μ-N^tBu)₂PE(NPh)-κN-κE]₂Zn} (E = S (11), Se (12), N-p-tolyl (13)). A crystal-structure analysis of 11 revealed a linear tetraspirocycle with a tetrahedrally coordinated, central zinc atom.