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

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 A(PH2)2 3; the latter reacts with Me3SnF at the glass-wall to give the first perstannylphosphonium pentafluorosilicate [P(SnMe3)4]+SiF5^– 4.