Catalytic dehydrocoupling of thienyl/furyl-substituted carbosilanes – Synthesis and characterization of functional poly(hydrosilane)s [RMe2Si(CH2)xSiH]n, (R=2-Th, 4-Me-2-Th, 2-Fu, 5-Me-2-Fu; x=2 and 3)

Organosilanes as synthetic precursors for oligosiloxanes and phenylsilica spheres

“…By following the procedure reported earlier, 29 the diorganosilanes, RR 1 SiH 2 (R, R 1 = Me, Ph; Me, cyclo -Hex), were synthesized by the reduction of corresponding dichlorodiorganosilanes with lithium aluminium hydride in diethyl ether. n -Hexylsilane was prepared by a similar reduction reaction using trichloro(hexyl)silane.…”

Linear, branched and network polysilanes with thienyl/furyl substituted sila-alkyl side chains and their applications for the synthesis of fluorescent silver nanoparticles/clusters

“…x SiH] n (R = 2-Th, 4-Me-2-Th, ref. 22 ) involves the reaction of the carbosilane precursors, RMe 2 Si(CH 2 ) x SiH 3 (20 mmol) with Cp 2 TiCl 2 (0.13 g, 0.52 mmol) and n-BuLi (0.71 mL, 1.6 M in hexane) at 50 • C. 22 The reaction turns blue in colour suggesting the onset of dehydrocoupling. The content in each case was kept in open till the catalyst becomes deactivated and the intense blue colour disappears.…”

“…During a systematic study on Ti-catalysed dehydrocoupling of various primary organosilanes, 17,18 it is observed that 2-thienylsilane or 2-furylsilane in presence of Cp 2 TiCl 2 /n-BuLi as catalyst does not undergo catenation while similar reactions proceed smoothly x SiH] n with average molecular weight (M w ) ranging between 1.6-2.6 × 10 3 (scheme 2). 22 A plausible mechanism based on previously known σ -bond metathesis pathway 27 has been proposed to explain preferential affinity of the carbosilanes towards dehydrogenative coupling. It has been suggested that passive nature of 2-thieny/2-furylsilane towards dehydrocoupling results from intramolecular coordinative association of the sulphur atom with [Ti] centre associated with intermediate metal-silyl complex, Cp 2 M(H)(SiH 2 R) (M = Ti, R = 2-Th) which prevents step growth polymerization process in these monomers.…”

Inorganic and organometallic polymers

“…44 The dehydrocoupling of the primary silanes, RMe 2 Si(CH 2 ) x SiH 3 (x = 2 and 3), using a Cp 2 TiCl 2 /2.2 n BuLi catalyst mixture, afforded various poly(hydrosilanes), such as 9, in moderate yields. 45 Poly[methylhydrosilane-co-diphenylsilane]s were prepared; interestingly these materials can act as photosensitizers for the generation of singlet oxygen upon exposure to visible light. 46 Ordered silica nanodot arrays were prepared from the photodegredation of poly(styrene-block-carbosilane) films.…”