Reaktionen an Silicium‐Silicium‐Bindungen, 2[1] Trichlorsilylierung von tert‐Butyldichlorphosphan und tert‐Butylbis(trimethylsilyl)phosphan mit Hexachlordisilan: Ein Weg zu neuen bifunktionellen (Trichlorsilyl)phosphanen

Abstract

Reactions of Silicon‐Silicon Bonds, 2[1]. – Trichlorosilylations of tert‐Butyldichlorophosphane and tert‐Butylbis(trimethylsilyl)phosphane with Hexachlorodisilane: Synthesis of New Bifunctional (Trichlorosilyl)phosphanesDi‐tert‐butyl(trimethylsilyl)phosphane (1) and tert‐butylbis(trimethylsilyl)phosphane (3) react with one equivalent of hexachlorodisilane with exchange of one trimethylsilyl group by a trichlorosilyl group under mild conditions to give di‐tert‐butyl(trichlorosilyl)phosphane (2) and tert‐butyl(trichlorosilyl)(trimethylsilyl)phosphane (4) in fair yields. tert‐Butylbis(trichlorosilyl)phosphane (5) is available from tert‐butyldichlorophosphane without organometallic reagents and solvents by simple reductive trichlorosilylation with the help of two equivalents of hexachlorodisilane. 5 is a useful precursor for phosphaalkane synthesis: with pivaloyl chloride, 5 leads to tert‐butyl‐[tert‐butyl(trichlorosilyloxy)methylene]phosphane (6). From 4 with pivaloyl chloride mainly 6 and some known tert‐butyl[tert‐butyl(trimethylsilyloxy)methylene]phosphane (7) are formed.