Triple para-substitution reactions of B(C6F5)3 and [(C6F5)3PF]+ with P(SiMe3)3

Abstract

para-Substitution reactions on C₆F₅ rings of Lewis acids have been exploited to achieve triply substituted derivatives. The reaction of B(C₆F₅)₃ with P(SiMe₃)₃ ultimately affords the Lewis acid B(C₆F₄P(SiMe₃)₂)₃1. This species binds Lewis bases affording the adducts LB(C₆F₄P(SiMe₃)₂)₃ (L = MeCN 2, OPEt₃3, PMe₃4, PBu₃5) and reacts with LiMe to give the salt [Li][MeB(C₆F₄P(SiMe₃)₂)₃]·3THF 6. It also reacts with H₂O to give (L)B(C₆F₄PH₂)₃ (L = H₂O 7, MeCN 8). In an analogous fashion, [(C₆F₅)₃PF][B(C₆F₅)₄] was converted to [FP(C₆F₄P(SiMe₃)₂)₃] [B(C₆F₅)₄] 9 and subsequently to [(MeO)P(C₆F₄PH₂)₃][B(C₆F₅)₄] 10.