Neutral and cationic group 13 phosphinimine and phosphinimide complexes

Reactions of the silylphosphimines R3PNSiMe3 (R = i-Pr, Ph, Cy) with AlCl3, AlMeCl2, AlMe2Cl, and AlMe3 afford the compounds (i-Pr3PNSiMe3)A1C13 (1), (R3PNSiMe3)AlMeCl2 (R = i-Pr, 2; Ph, 3; Cy, 4), (R3PNSiMe3)AlMe2Cl (R = i-P r, 5; Ph, 6; Cy, 7), and (R3PNSiMe3)AlMe3 (R = i-Pr, 8; Ph, 9; Cy, 10). Rea ction of R3PNH (R = t-Bu, Cy, Ph) with AlMe2Cl and AlMe3 afforded (R3PNH)Al Me2Cl (R = Cy, 11; t-Bu, 12) and (Ph3PNH)AlMe3 (13), respectively. The dime ric species [Me2Al(mu-NPt-Bu-3)](2) (14) [AlCl2(mu-NPt-Bu-3)](2) (15) were derived from reactions of(t-Bu3PNH) and AlMe3 and t-Bu3PNLi and MeAlCl2, re spectively. Reaction of the bisphosphinimine salt LiCH(PPh2(NSiMe3))(2) (16 ) with aluminum, gallium, and indium halides yielded [CH(PPh2(NSiMe3)(2)]MC l2 (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 compound s [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 of 17-19 with t he appropriate alkylating reagents. The borane B(C6F5)(3) reacts stoichiome trically with the adducts 8-10 to give the products [(R3PNSiMe3)AlMe2] [MeB (C6F5)(3)] (R = i-Pr, 26; Ph, 27; Cy, 28) while treatment of 27 with PMe3 a ffords clean conversion to the salt [(Ph3PNSiMe3)(2)AlMe(PMe3)][(MeB(C6F5)( 3))] (29). Similarly, species [Me2Al(mu-NPt-Bu-3)(2)AlMe][MeB(C6F5)(3)] (30 ) and [Me2Al(mu-NPt-Bu-3)(2)AlMe(PMe3)][MeB(C6F5)(3)] (31) were obtained fr om 14. Attempts to generate the related ionic derivatives from 20-25 yielde d unstable mixtures of products. Under mild conditions these group 13 ionic species did not effect the polymerization of ethylene. Crystallographic da ta are reported for compounds 1, 3, 6, 8, 11, 13-15, 18, and 20.