Small organosilicon molecules - Synthesis, stereochemistry, and reactivity

Systematic studies have been continued in the chemistry of simple silylated hydrocarbons of the alkane, alkene, alkyne, and arene series. Polysilylated species with SiH₃ groups have been the main synthetic target. Through their low molecular mass, high volatility, and specific thermal, plasma or photochemical fragmentation behavior, these species are promising precursors for the production of tailored materials based on the ternary system Si-C-H or even the binary system Si-C. The prototypes studied previously included the poly(silyl)methanes (H₃Si)_nCH_4-n -ethenes (H₃Si)_n2H_4-n and -ethynes H₃SiC=CX (X = H₃ Hal). This chemistry has now been extended to poly(silyl)arenes from the benzene and naphthalene series: The Merker-Scott type reaction of the appropriate halohydrocarbon with aryldihydrohalosilanes and magnesium in THF affords suitable arylated precursors, which are readily converted into the hydrogenated products through regioselective Si-aryl cleavage by strong acid, followed by hydride reduction. Crystal structures of the arylated precursors and the simple silyl compounds have been determined for selected examples. Nitrogen- and/or oxygen-containing molecules (quaternary systems such as silyl-amines, silyl-hydrazines, (hetero)siloxanes, and silyl-hydroxylamines) have also been considered and some new prototypes investigated, i.e., small molecules from the Si/N/C/H, Si/O/C/H, and Si/N/O/C/H systems, respectively.