Some Selective Reactions of the Silicon-Hydrogen Group With Organometallic Compounds

Silacyclobutane‐Based Diblock Copolymers with Vinylferrocene, Ferrocenylmethyl Methacrylate, and [1]Dimethylsilaferrocenophane

“…Throughout, the latter values were in good agreement with the applied monomer‐to‐initiator ratios. Although approaching high molar masses was not an issue in the case of 8b , it proved practically impossible to obtain products with really low PDIs: usually, values of 1.5–2.0 were found as the result of chain‐transfer reactions involving the hydrogens attached to the silicon atoms:30, 32, 33 anionic ring‐opening polymerization of MSB is assumed to proceed similar to what has been proposed for anionic polymerization of DMSB:43, 44 the first step is nucleophilic attack of an anion on the silyl center of a monomer. The formed pentacoordinate siliconate anion triggers opening of the silacyclobutane ring, which results in an open‐chain primary carbanion.…”

“…Therefore, it was our goal to identify the measures that allow adaptation of the state‐of‐the‐art homopolymerization recipes to the specific requirements of the syntheses of copolymers such as 9 – 11 . In the present paper, we focus on 1,1‐dimethylsilacyclobutane (DMSB) 7a as the carbosilane comonomer, but additionally discuss some trial studies on 1‐methylsilacyclobutane (MSB) 7b : access to copolymers containing segments of the latter monomer was assumed to be more complicated due its susceptibility to side reactions 30, 32, 33. On the other hand, the resulting PMSB segments bear a hydrogen atom on every silicon, which might open up access to versatile hydrosilylation strategies.…”

Silicon Compounds, Organic

“…The reactivity is particularly high in THF. In this solvent, vinyl groups have been introduced for the first time by using vinylmagnesium bromide [48], and SiÀH groups can be substituted with alkyl groups [49].…”

Organosilanes

“…They polymerise o n heating, particularly i n the presence o f a catalyst, but this process can be reversed at higher temperature i f no cross-linking has occurred. Hydrolysing methylphenyldichlorosilane gives two cyclotrisiloxanes and four cyclotetrasiloxanes, and all have been synthesised separately f r o m either the meso or racemic form o f the hydroxydisiloxane (452) using methylphenyldichlorosilane or a meso / mccmic mixture o f the chlorodisiloxane (453 663 ' 664 The production o f silicones i s described more extensively later (Section 9.3.4).…”