Reactions of tris(dimethylsilyl)methane and polymers containing si—h groups with various hydroxy compounds under aerobic and mild conditions

Abstract

Tris(dimethylsilyl)methane, (HMe2Si) 3 −CH, reacts with n‐propyl, iso‐propyl, n‐butyl, s‐butyl, iso‐butyl, n‐pentyl, s‐pentyl, n‐hexyl alcohol, and phenol in the presence of chloroplatinic acid (H2PtCl6ċ6H2O) in air to give products (ROMe2Si)3CH (where R is n‐propyl, iso‐propyl, n‐butyl, s‐butyl, iso‐butyl, n‐pentyl, s‐pentyl, n‐hexyl, phenyl). Similar reactions with benzyl alcohol and acetic acid lead to the unexpected products, (PhCH2)2O and HC(Me2SiOSiMe2)3CH, respectively. The compound (n‐BuOMe2Si)3CSiMe2H was made from (n‐BuOMe2Si)3CH by treatment with lithium diisopropylamide, followed by quenching with HMe2SiCl. The homopolymer poly{(4‐chloromethyl)styrene} and copolymers with styrene (in 1:1 and 1:3 mol ratio) were synthesized by free radical polymerization, and (HMe2Si)3C groups were linked to them by nucleophilic substitution reactions between (HMe2Si)3CLi and the chloromethyl groups of the polymer side chains. The resulting functional polymers containing Si—H bonds reacted with various alcohols in the presence of chloroplatinic acid under heterogeneous conditions. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:365–376, 2008; Published online in Wiley InterScience (http://www.interscience.wiley.com). DOI 10.1002/hc.20440

A linear cobalt(II) complex with maximal orbital angular momentum from a non-Aufbau ground state

“…OPh)3 , which has been reported previously using a different synthetic method(45). The identity of HC(SiMe 2 OPh) 3 was confirmed by 1 H NMR spectroscopy.…”

Facile route to synthesis of functionalised poly(methylalkoxy)siloxane under mild and aerobic conditions in the presence of platinum catalysts

“…The former Platinum catalyst at Pt VI oxidation state, H 2 PtCl 6 , 6H 2 O, is Speier's catalyst and the latter Platinum catalyst at Pt 0 oxidation state is Karstedt's catalyst [Pt(0)-divinyltetramethyldisiloxane complex]. Regarding to our recent paper in which we have reported the preparation of tris(alkoxydimethylsilyl)methanes via the alcoholysis reaction of tris(dimethylsilyl)methane and various alcohols in the presence of H 2 PtCl 6 Á6H 2 O as catalyst under mild and aerobic conditions [25] (Scheme 1). We were interested in extending the applied methodology in the grafting of PMHS with various alcohols.…”

Synthesis of 1,1-bis(silyl)-1-alkene derivatives bearing Si–H functional groups via Peterson protocol

“…Recently, we have embarked on a program directed towards the development of tris(dimethylsilyl)methyllithium, (HMe 2 Si) 3 CLi, reaction for the generation of synthetically useful organosilicon compounds [18,19]. We paid particular attention to epoxides because of their ring opening reaction and the potentially coordination of the produced alkoxide group to silicon, thereby enabling the facile cyclization.…”