The Function of the Trimethylsilyl Substituent in the Syntheses of Low‐Valent Phosphorus and Arsenic Containing Compounds

Simple conversion of trisodium phosphide, Na3P, into silyl- and cyanophosphides and the structure of a terminal silver phosphide

“…Silylated phosphanes and phosphides are useful building blocks in phosphorus chemistry 1 and are soluble in organic solvents and suited to replace PH 3 or M[PH 2 ] which are mostly insoluble and difficult to handle. 2 Particularly, tris(trimethylsilyl)phosphane P(TMS) 3 3 1 (TMS = SiMe 3 ) and the alkali metal salts M[P(TMS) 2 ] M [2] (M = Li, Na, K) are highly popular 4 but their preparation requires a sodium-potassium alloy 5 or phosphine gas which are hazardous materials. 6 Tris (triphenylsilyl)phosphane 3 7 and the phosphides M[P(SiPh 3 ) 2 ] M[4] 8 were prepared via silylation of a metal phosphide produced from elemental phosphorus and a Na/K alloy but their chemistry remains unexplored (Scheme 1).…”

“…We investigated whether a trimethylsilyl-substituted equivalent of [7] − would be accessible via the reaction of Na [2] with trimethylsilyl isocyanate in THF. The product of this reaction was identified as P(TMS) 3 1 via 31 P-and 13 C-NMR.…”