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

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