[SiS_xH_y]_n – Perhydridopolysilathianes: Cross‐Linked Thio Analogues of Polysiloxanes

Abstract

Polysiloxane‐analogous Si–S compounds have so far not been reported. Transsilylation reactions of the solid pyridine adduct of HSiCl3 with gaseous Me3Si–S–SiMe3 yielded perhydridopolysilathianes. 29Si NMR, FTIR, and Raman spectroscopy; elemental and thermal analysis; XRD; SEM; and gas‐adsorption measurements indicated that the product consists of D‐, T‐, and Q‐units with a composition of ([H2SiS]1.2[HSiS1.5]2.6[SiS2]1.0)n. Formation of the latter is caused by pyridine‐catalyzed dismutation reactions. The polymer is mesoporous with a surface area of 187 m2 g–1; furthermore, it is amorphous and insoluble in organic solvents.

A Non-Hydrolytic Sol–Gel Route to Organic-Inorganic Hybrid Polymers: Linearly Expanded Silica and Silsesquioxanes

“…Interesting nanostructured sulfide materials have been obtained from molybdenum chloride and S(Si(CH 3 ) 3 ) 2 in chloroform [ 42 ]. A similar approach, that is also based on the formation of trimethylchlorosilane, has been used to generate polydimethylsiloxane (PDMS) analogous silicon-sulfur polymers [ 43 ].…”