Neutral and Cationic Group 13 Phosphinimine and Phosphinimide Complexes

Abstract

Reactions of the silylphosphimines R 3 PNSiMe 3 (R = i -Pr, Ph, Cy) with AlCl 3, AlMeCl 2, AlMe 2 Cl, and AlMe 3 afford the compounds ( i -Pr 3 PNSiMe 3 )AlCl 3 ( 1 ), (R 3 PNSiMe 3 )AlMeCl 2 (R = i -Pr, 2; Ph, 3; Cy, 4 ), (R 3 PNSiMe 3 )AlMe 2 Cl (R = i -Pr, 5; Ph, 6; Cy, 7 ), and (R 3 PNSiMe 3 )AlMe 3 (R = i -Pr, 8; Ph, 9; Cy, 10 ). Reaction of R 3 PNH (R = t- Bu, Cy, Ph) with AlMe 2 Cl and AlMe 3 afforded (R 3 PNH)AlMe 2 Cl (R = Cy, 11; t -Bu, 12 ) and (Ph 3 PNH)AlMe 3 ( 13 ), respectively. The dimeric species [Me 2 Al(μ-NP t -Bu 3 )] 2 ( 14 ) [AlCl 2 (μ-NP t -Bu 3 )] 2 ( 15 ) were derived from reactions of ( t -Bu 3 PNH) and AlMe 3 and t- Bu 3 PNLi and MeAlCl 2, respectively. Reaction of the bisphosphinimine salt LiCH(PPh 2 (NSiMe 3 )) 2 ( 16 ) with aluminum, gallium, and indium halides yielded [CH(PPh 2 (NSiMe 3 )) 2 ]MCl 2 (M = Al, 17; Ga, 18; In, 19 ) while the analogous species [CH(PPh 2 (NSiMe 3 )) 2 ]AlMe 2 ( 20 ) was prepared via reaction of 16 with Me 2 AlCl. The compounds [CH(PPh 2 (NSiMe 3 )) 2 ]MR 2 (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 the appropriate alkylating reagents. The borane B(C 6 F 5 ) 3 reacts stoichiometrically with the adducts 8 − 10 to give the products [(R 3 PNSiMe 3 )AlMe 2 ][MeB(C 6 F 5 ) 3 ] (R = i -Pr, 26; Ph, 27; Cy, 28 ) while treatment of 27 with PMe 3 affords clean conversion to the salt [(Ph 3 PNSiMe 3 ) 2 AlMe(PMe 3 )][(MeB(C 6 F 5 ) 3 )] ( 29 ). Similarly, species [Me 2 Al(μ-NP t -Bu 3 ) 2 AlMe][MeB(C 6 F 5 ) 3 ] ( 30 ) and [Me 2 Al(μ-NP t -Bu 3 ) 2 AlMe(PMe 3 )][MeB(C 6 F 5 ) 3 ] ( 31 ) were obtained from 14 . Attempts to generate the related ionic derivatives from 20 − 25 yielded unstable mixtures of products. Under mild conditions these group 13 ionic species did not effect the polymerization of ethylene. Crystallographic data are reported for compounds 1, 3, 6, 8, 11, 13 − 15, 18, and 20 .