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- W1186536418 abstract "This chapter discusses redistributions catalyzed by transition-metal complexes. Redistribution, or disproportionation, constitutes an important class of reactions in organosilicon chemistry. Redistributions on silicon may be initiated by thermolysis or by catalytic activation at somewhat lower temperatures. In the gas phase, methyl is transferred from Men SiH4–n, to CH3+ almost as readily as hydrogen. Silacyclobutanes with metal substituents may also be polymerized to give novel polymers with pendant metal groups. By using chiral silyl hydrides, it has been demonstrated that the exchanges occur with the retention of configuration at silicon. The complete lack of isomerization of the p-tolyl group during the disproportionation of Ar3SiH is noteworthy. Similarly, the vinyl group of trimethylvinylsilane is hydrolyzed by a catalytic amount of Zeise's salt [(C2H4)PtC13]- in moist acetone. The redistribution reactions of hydridodisilanes of the type R3SiSiR2H are more varied than those of the corresponding monosilanes. In redistribution reactions catalyzed by transition-metal complexes, di- or polysiloxanes are expected to share some characteristics of both monosilanes and di- or polysilanes. Thus, the availability of the four-membered metallacycle in the catalytic cycle greatly enhances the rate of disproportionation of tetramethyldisiloxane. Some of these catalytic cycles lead to products that appear to arise from divalent silylenoid species." @default.
- W1186536418 created "2016-06-24" @default.
- W1186536418 creator A5018765847 @default.
- W1186536418 creator A5037317469 @default.
- W1186536418 date "1981-01-01" @default.
- W1186536418 modified "2023-10-17" @default.
- W1186536418 title "Redistribution Reactions on Silicon Catalyzed by Transition Metal Complexes" @default.
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- W1186536418 doi "https://doi.org/10.1016/s0065-3055(08)60368-8" @default.
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