Syntheses and structures of P-anilino-P-chalcogeno- and P-anilino-P-iminodiazasilaphosphetidines and their group 12 and 13 metal compounds

摘要

The P-anilino-P-chalcogeno(imino)diazasilaphosphotidines [Me2S(mu-N'Bu)(2)P=E(NHPh)] (E = O (3), S (4), Se (5), N-p-tolyl (6)) were synthesized by oxidizing the P-anilinodiazasilaphosphetidine [Me2Si((NBu)-Bu-t)(2)P(NHPh)] (2) with cumene hydroperoxide, sulfur, selenium, and p-tolyl azide, respectively. The lithium salt of 4 reacted with thallium monochloride to produce {[Me2Si(mu-(NBu)-Bu-t)(2)P=S(NPh)-kappaN-kappaS]Tl} (7), which features a two-coordinate thallium atom. Treatment of 4-6 with AlMe3 gave the monoligand dimethylaluminum complexes {[Me2Si(mu-(NBu)-Bu-t)(2)P=E(NPh)-kappaN-kappaE]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(mu-(NBu)-Bu-t)(2)P= E(NPh)-kappaN-kappaE](2)Zn} (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. [References: 61]