Synthesis of the first fluoro(phosphanyl)- and diphosphanyl-stannanes and surprising formation of [P(SnMe3)4]+SiF5−

Abstract

Monophosphanylation of the difluorostannane Is₂SnF₂ (Is = 2,4,6-triisopropylphenyl) with Si(PH₂)₄ furnishes the first isolable fluoro(phosphanyl)stannane Is₂Sn(F)PH₂ 1, which readily undergoes unique SiO₂-assisted decompostion to [Is₂Sn(PH)]₂ 2 and HF, while further phosphanylation of 1 leads to the remarkably stable diphosphanylstannane Is₂Sn(PH₂)₂ 3; the latter reacts with Me₃SnF at the glass-wall to give the first perstannylphosphonium pentafluorosilicate [P(SnMe₃) ₄]⁺SiF₅⁻ 4.