1072-14-6Relevant articles and documents
Reaction of allylamine with hexylsilane
Storozhenko,Belyakova,Knyazev,Shutova,Khromykh,Starikova,Chernyshev
, p. 220 - 224 (2006)
The reaction of hexylsilane with allylamine is accompanied by the liberation of hydrogen and formation of allylaminosilanes and compounds with the Si-Si bond. The hydrosilylation pathway virtually is not realized. The B3LYP/6-311G**calculations show that all the considered reactions are thermodynamically allowed. Pleiades Publishing, Inc., 2006.
Alkenylsilane effects on organotitanium-catalyzed ethylene polymerization. Toward simultaneous polyolefin branch and functional group introduction
Amin, Smruti B.,Marks, Tobin J.
, p. 4506 - 4507 (2006)
The comonomer 5-hexenylsilane is introduced into organotitanium-mediated ethylene polymerizations to produce silane-terminated ethylene/5-hexenylsilane copolymers. The resulting polymers were characterized by 1H and 13C NMR, GPC, and DSC. High activities (up to 107 g polymer/(mol Ti·atm ethylene·h)) and narrow polydispersities are observed in the polymerization/chain transfer process. Ethylene/5-hexenylsilane copolymer molecular weights are found to be inversely proportional to 5-hexenylsilane concentration, supporting a silanolytic chain transfer mechanism. Control experiments indicate that chain transfer mechanism by 5-hexenylsilane is significantly more efficient than that of n-hexylsilane for organotitanium-mediated ethylene polymerization. The present study represents the first case in which a functionalized comonomer is efficiently used to effect both propagation and chain transfer chemistry during olefin polymerization. Copyright
CO Displacement in an Oxidative Addition of Primary Silanes to Rhodium(I)
Biswas, Abhranil,Ellern, Arkady,Sadow, Aaron D.
, (2019/03/11)
The rhodium dicarbonyl {PhB(Ox Me2)2ImMes}Rh(CO)2 (1) and primary silanes react by oxidative addition of a nonpolar Si-H bond and, uniquely, a thermal dissociation of CO. These reactions are reversible, and kinetic measurements model the approach to equilibrium. Thus, 1 and RSiH3 react by oxidative addition at room temperature in the dark, even in CO-Saturated solutions. The oxidative addition reaction is first-Order in both 1 and RSiH3, with rate constants for oxidative addition of PhSiH3 and PhSiD3 revealing kH/kD a 1. The reverse reaction, reductive elimination of Si-H from {PhB(Ox Me2)2ImMes}RhH(SiH2R)CO (2), is also first-Order in [2] and depends on [CO]. The equilibrium concentrations, determined over a 30 °C temperature range, provide ?"H° = a'5.5 ± 0.2 kcal/mol and ?"S° = a'16 ± 1 cal·mol-1K-1 (for 1 a?., 2). The rate laws and activation parameters for oxidative addition (?"Ha§§ = 11 ± 1 kcal·mol-1 and ?"Sa§§ = a'26 ± 3 cal·mol-1·K-1) and reductive elimination (?"Ha§§ = 17 ± 1 kcal·mol-1 and ?"Sa§§ = a'10 ± 3 cal·mol-1K-1), particularly the negative activation entropy for both forward and reverse reactions, suggest the transition state of the rate-Determining step contains {PhB(Ox Me2)2ImMes}Rh(CO)2 and RSiH3. Comparison of a series of primary silanes reveals that oxidative addition of arylsilanes is ca. 5× faster than alkylsilanes, whereas reductive elimination of Rh-Si/Rh-H from alkylsilyl and arylsilyl rhodium(III) occurs with similar rate constants. Thus, the equilibrium constant Ke for oxidative addition of arylsilanes is >1, whereas reductive elimination is favored for alkylsilanes.
METHOD FOR PRODUCING HYDROSILANE USING BORANE REDUCTION
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Paragraph 0025, (2018/07/28)
PROBLEM TO BE SOLVED: To provide a method for producing hydrosilane that can efficiently produce the hydrosilane. SOLUTION: In the presence of a Lewis base, a silane having a structure represented by a formula (a) reacts with a borane complex or diborane, to efficiently produce hydrosilane (in the formula (a), R1 is a C1 to C20 hydrocarbon group, or a C1 to C10 acyl group). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT