Three new nortricyclic P 7 R 3 derivatives with R = (SiMe 3 ) 2 -MeSi-(2), (SiMe 3 ) 2 PhSi-(3), and cyclo-Si 6 Me 11 -(4) were synthesized from red phosphorus, sodium/potassium alloy, and a chlorooligosilane, and their structures were elucidated with X-ray diffraction. Reactions of 2 and 3 and of tri(hypersilyl)heptaphosphane 1 [hypersilyl = (SiMe 3 ) 3 Si-] with KOtBu and LiOtBu were performed, which led to different results depending on the size of the substituent. With KOtBu, Si-P bonds were cleaved in 2 and 3, and the mono-and dianions [
18-crown-6]+ salt of 2b suitable for X-ray diffraction could be grown successfully. Compound 1 reacted in an unprecedented way with KOtBu at -60°C. An Si-Si bond was cleaved, and a transient silyl anion formed, which immediately rearranged into a transient heptaphosphanide anion [Hyp 2 P 7 ] -(1a) under expulsion of bis(trimethylsilyl)silylene.
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