Boron and Aluminum Complexes of Sterically Demanding Phosphinimines and Phosphinimides

Reactions of sterically demanding phosphinimines R3PNH [R = i-Pr (1), t-Bu (2)] were examined. Reactions with
B(C6F5)3 formed the adducts (R3PNH)B(C6F5)3 [R = i-Pr (3), t-Bu (4)] in high yield. On the other hand, 2 reacts
with HB(OBu)2, evolving H2 to give t-Bu3PNB(OBu)2 (5). The reaction of 2 equiv of 2 with BH3·SMe2 affords the
species (t-Bu3PN)2BH (6). In contrast, the reaction of n-Bu(t-Bu)2PNH with BH3·SMe2 results in the formation of the
robust adduct n-Bu(t-Bu)2PNH·BH3 (8). An alternative route to borane−phosphinimide complexes involves Me3SiCl
elimination, as exemplified by the reaction of BCl2Ph with n-Bu3PNSiMe3, which gives the product n-Bu3PNBCl(Ph)
(9). The corresponding reactions of the parent phosphinimines 1 and 2 with AlH3·NMe2Et give the dimers [(μ-i-Pr3PN)AlH2]2 (10) and [(μ-t-Bu3PN)AlH2]2 (11). Species 11 reacts further with Me3SiO3SCF3 to provide [(μ-t-Bu3PN)AlH(OSO2CF3)]2 (12). The reaction of the lithium salt [t-Bu3PNLi]4 (13) with BCl3 proceeds smoothly to give
t-Bu3PNBCl2 (14), which is readily alkylated to give t-Bu3PNBMe2 (15). Subsequent reaction of 15 with B(C6F5)3
results in methyl abstraction and the formation of [(μ-t-Bu3PN)BMe]2[MeB(C6F5)3]2 (16). The reaction of 13 in a 2:1
ratio with BCl3 gives the salt [(t-Bu3PN)2B]Cl (17). This species can be methylated to give (t-Bu3PN)2BMe (18),
which undergoes subsequent reaction with [Ph3C][X] (X = [B(C6F5)4], [PF6]) to form the related salts [(t-Bu3PN)2B][B(C6F5)4] (19) and [(t-Bu3PN)2B][PF6] (20), respectively. Analogous reactions with [Ph3C][BF4] afforded [t-Bu3PNBF2]2 (21). Compounds 3, 4, 6, 8, 11, 12, 17, 19, and 21 were characterized by X-ray crystallography.