Neutral and Cationic Group 13 Phosphinimine and Phosphinimide Complexes

Abstract

Reactions of the silylphosphimines R3PNSiMe3 (R = i-Pr, Ph, Cy) with AlCl3, AlMeCl2, AlMe2Cl, and AlMe3 afford the compounds (i-Pr3PNSiMe3)AlCl3 (1), (R3PNSiMe3)AlMeCl2 (R = i-Pr, 2; Ph, 3; Cy, 4), (R3PNSiMe3)AlMe2Cl (R = i-Pr, 5; Ph, 6; Cy, 7), and (R3PNSiMe3)AlMe3 (R = i-Pr, 8; Ph, 9; Cy, 10). Reaction of R3PNH (R = t-Bu, Cy, Ph) with AlMe2Cl and AlMe3 afforded (R3PNH)AlMe2Cl (R = Cy, 11; t-Bu, 12) and (Ph3PNH)AlMe3 (13), respectively. The dimeric species [Me2Al(μ-NPt-Bu3)]2 (14) [AlCl2(μ-NPt-Bu3)]2 (15) were derived from reactions of (t-Bu3PNH) and AlMe3 and t-Bu3PNLi and MeAlCl2, respectively. Reaction of the bisphosphinimine salt LiCH(PPh2(NSiMe3))2 (16) with aluminum, gallium, and indium halides yielded [CH(PPh2(NSiMe3))2]MCl2 (M = Al, 17; Ga, 18; In, 19) while the analogous species [CH(PPh2(NSiMe3))2]AlMe2 (20) was prepared via reaction of 16 with Me2AlCl. The compounds [CH(PPh2(NSiMe3))2]MR2 (M = Al, Bz, 21; M = Ga, R = Me, 22; Bz, 23; M = In, R = Me, 24; Bz, 25) were readily prepared by treatment...