Reactivity of an Aryl-Substituted Silicon-Silicon Triple Bond: Reactions of a 1,2-Diaryldisilyne with Alkenes

Reactivity of an Aryl-Substituted Silicon-Silicon Triple Bond: Reactions of a 1,2-Diaryldisilyne with Alkenes
한준수Sasamori, TakahiroMizuhata, YoshiyukiTokitoh, Norihiro
disilyne; disilene; kinetic stabilization; disilacyclobutene
Issue Date
Journal of the American Chemical Society
VOL 132, NO 8, 2546-2547
Since the first isolation of a disilene (Mes2Si=SiMes2; Mes = 2,4,6-trimethylphenyl) in 1981 by West et al.,1a there have been many investigations of the chemistry of multiply bonded silicon compounds.1 In 2004, Sekiguchi’s and Wiberg’s groups independently reported two types of disilynes (RSi≡SiR: R = SiPri[CH(SiMe3)2]2,2a I; R = SiMe(SiBut 3)2,2b II), both of which are stabilized by bulky silyl substituents. As for the stabilization of the reactive Si-Si triple bond, theoretical calculations showed that significant stabilizing effects with the electropositive silyl group might be of great importance in addition to steric protection.3 Recently, we reported the synthesis and structure of a stable 1,2- diaryldisilyne, BbtSitSiBbt (1, Bbt = 2,6-bis[bis(trimethylsilyl- )methyl]-4-[tris(trimethylsilyl)methyl]phenyl).4 The triple-bond character of 1 was evaluated on the basis of the experimental results with the aid of detailed theoretical calculations, and it was suggested that the Si-Si triple bond in aryl-substituted disilyne 1 is weaker than those the silyl-substituted disilynes I and II.4 In order to understand the chemistry of the fascinating triply bonded organosilicon species, it is very important to investigate the unexplored reactivity of disilynes in detail. However, only a few reactions have been reported to date, probably because of the difficulty of synthesizing disilynes.2b,5-7 Because 1 is the first aryl-substituted disilyne, it will provide us with valuable information about how the substituent affects the reactivity of disilynes. In this paper, we describe unique results obtained from the reactions of bulky, arylsubstituted disilyne 1 with ethylene, cyclohexene, and 2,3-dimethyl- 1,3-butadiene.
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