40391-86-4

Upstream product

• 775-12-2 diphenylsilane 
• 67-64-1 acetone 
• 67-63-0 isopropyl alcohol 
• 1631-83-0 diphenylsilyl chloride 

Downstream Products

• 1013-91-8 fluoro(diphenyl)silane 
• 1555880-99-3 C₁₉H₂₂O₂Si 
• 1555881-18-9 C₂₀H₂₄O₂Si 
• 1555881-02-1 C₂₀H₂₂OSi 
• 1555880-86-8 C₂₁H₂₄OSi 
• 42073-22-3 Fluor-(4-nitrophenoxy)-diphenylsilan 

Relevant academic research and scientific papers

Hydrosilane σ-Adduct Intermediates in an Adaptive Zinc-Catalyzed Cross-dehydrocoupling of Si?H and O?H Bonds

Three-coordinate PhBOX (Formula presented.) ZnR (PhBOX (Formula presented.) =phenyl-(4,4-dimethyl-oxazolinato; R=Me: 2 a, Et: 2 b) catalyzes the dehydrocoupling of primary or secondary silanes and alcohols to give silyl ethers and hydrogen, with high turnover numbers (TON; up to 107) under solvent-free conditions. Primary and secondary silanes react with small, medium, and large alcohols to give various degrees of substitution, from mono- to tri-alkoxylation, whereas tri-substituted silanes do not react with MeOH under these conditions. The effect of coordinative unsaturation on the behavior of the Zn catalyst is revealed through a dramatic variation of both rate law and experimental rate constants, which depend on the concentrations of both the alcohol and hydrosilane reactants. That is, the catalyst adapts its mechanism to access the most facile and efficient conversion. In particular, either alcohol or hydrosilane binds to the open coordination site on the PhBOX (Formula presented.) ZnOR catalyst to form a PhBOX (Formula presented.) ZnOR(HOR) complex under one set of conditions or an unprecedented σ-adduct PhBOX (Formula presented.) ZnOR(H?SiR′3) under other conditions. Saturation kinetics provide evidence for the latter species, in support of the hypothesis that σ-bond metathesis reactions involving four-centered electrocyclic 2σ–2σ transition states are preceded by σ-adducts.

Photoactivated silicon-oxygen and silicon-nitrogen heterodehydrocoupling with a commercially available iron compound

Silicon-oxygen and silicon-nitrogen heterodehydrocoupling catalyzed by the commercially available cyclopentadienyl dicarbonyl iron dimer [CpFe(CO)2]2 (1) under photochemical conditions is reported. Reactions between alcohols and PhSi

Heavier Alkaline-Earth Catalyzed Dehydrocoupling of Silanes and Alcohols for the Synthesis of Metallo-Polysilylethers

The dehydrocoupling of silanes and alcohols mediated by heavier alkaline-earth catalysts, [Ae{N(SiMe3)2}2?(THF)2] (I–III) and [Ae{CH(SiMe3)2}2?(THF)2], (IV–VI) (Ae=Ca, Sr, Ba) is described. Primary, secondary, and tertiary alcohols were coupled to phenylsilane or diphenylsilane, whereas tertiary silanes are less tolerant towards bulky substrates. Some control over reaction selectivity towards mono-, di-, or tri-substituted silylether products was achieved through alteration of reaction stoichiometry, conditions, and catalyst. The ferrocenyl silylether, FeCp(C5H4SiPh(OBn)2) (2), was prepared and fully characterized from the ferrocenylsilane, FeCp(C5H4SiPhH2) (1), and benzyl alcohol using barium catalysis. Stoichiometric experiments suggested a reaction manifold involving the formation of Ae–alkoxide and hydride species, and a series of dimeric Ae–alkoxides [(Ph3CO)Ae(μ2-OCPh3)Ae(THF)] (3 a–c, Ae=Ca, Sr, Ba) were isolated and fully characterized. Mechanistic experiments suggested a complex reaction mechanism involving dimeric or polynuclear active species, whose kinetics are highly dependent on variables such as the identity and concentration of the precatalyst, silane, and alcohol. Turnover frequencies increase on descending Group 2 of the periodic table, with the barium precatalyst III displaying an apparent first-order dependence in both silane and alcohol, and an optimum catalyst loading of 3 mol % Ba, above which activity decreases. With precatalyst III in THF, ferrocene-containing poly- and oligosilylethers with ferrocene pendent to- (P1–P4) or as a constituent (P5, P6) of the main polymer chain were prepared from 1 or Fe(C5H4SiPhH2)2 (4) with diols 1,4-(HOCH2)2-(C6H4) and 1,4-(CH(CH3)OH)2-(C6H4), respectively. The resultant materials were characterized by NMR spectroscopy, gel permeation chromatography (GPC) and DOSY NMR spectroscopy, with estimated molecular weights in excess of 20,000 Da for P1 and P4. The iron centers display reversible redox behavior and thermal analysis showed P1 and P5 to be promising precursors to magnetic ceramic materials.

Dehydrogenative coupling of alcohols and carboxylic acids with hydrosilanes catalyzed by a salen-Mn(v) complex

A Mn(v)-salen complex was found to be an effective catalyst for the dehydrogenative coupling of hydroxyl groups with hydrosilane. The reaction conditions were optimized with different silanes and efficient dehydrogenative coupling was achieved by using triethoxysilane and diphenylsilane. Various alcohols and phenols and a limited number of carboxylic acids were converted into the corresponding silyl ethers and silyl esters. A range of functional groups such as chloro, nitro, methoxy, carbonyl and carbon-carbon multiple bonds are tolerated in the reaction.

Hydrosilylation of Aldehydes and Ketones Catalyzed by a Terminal Zinc Hydride Complex, [κ3-Tptm]ZnH

Tris(2-pyridylthio)methyl zinc hydride, [κ3-Tptm]ZnH, is an effective catalyst for multiple insertions of carbonyl groups into the Si-H bonds of PhxSiH4-x (x = 1, 2). Specifically, [κ3-Tptm]ZnH catalyzes the insertion of a variety of aldehydes and ketones into the Si-H bonds of PhSiH3 and Ph2SiH2 to afford PhSi[OCH(R)R′]3 and Ph2Si[OCH(R)R′]2, respectively. The mechanism for hydrosilylation is proposed to involve insertion of the carbonyl group into the Zn-H bond to afford an alkoxy species, followed by metathesis with the silane to release the alkoxysilane and regenerate the zinc hydride catalyst. Multiple insertion of prochiral ketones results in the formation of diastereomeric mixtures of alkoxysilanes that can be identified by NMR spectroscopy.

Beyond the roche ester: A new approach to polypropionate stereotriad synthesis

An efficient, step-economical, and scalable approach to the synthesis of polypropionate stereotriads has been developed. Either 2-butyne or propyne is subjected to rhodium-catalyzed silylformylation and in situ crotylation of the resulting aldehydes. Tamao oxidation under either standard conditions or aprotic conditions then delivers the completed stereotriads in a three-step, two-pot sequence. In contrast to the classical Roche ester approach, the α-stereocenter is obtained for free.

POP-pincer silyl complexes of group 9: Rhodium versus iridium

9,9-Dimethyl-4,5-bis(diisopropylphosphino)xanthene (xant(P iPr2)2) derivatives RhCl{xant(P iPr2)2} (1) and IrHCl{xant(PiPr 2)[iPrPCH(Me)CH2]} (2) react with diphenylsilane and triethylsilane to give the saturated d6-compounds RhHCl(SiR3){xant(PiPr2)2} (SiR 3 = SiHPh2 (3), SiEt3 (4)) and IrHCl(SiR 3){xant(PiPr2)2} (SiR3 = SiHPh2 (5), SiEt3 (6)). Complexes 3 and 5 undergo a Cl/H position exchange process via the MH{xant(PiPr2) 2} (M = Rh (8), Ir (E)) intermediates. The rhodium complex 3 affords the square planar d8-silyl derivative Rh(SiClPh2) {xant(PiPr2)2} (7), whereas the iridium derivative 5 gives IrH2(SiClPh2){xant(PiPr 2)2} (9), which is stable. In agreement with the formation of 7, the reactions of 8 with silanes are a general method to prepare square planar d8-rhodium-silyl derivatives. Thus, the addition of triethylsilane and triphenylsilane to 8 initially leads to the dihydrides RhH2(SiR3){xant(PiPr2)2} (SiR3 = SiEt3 (10), SiPh3 (11)), which lose molecular hydrogen to afford Rh(SiR3){xant(PiPr 2)2} (SiR3 = SiEt3 (12), SiPh 3 (13)). Treatment of 7 with NaBArF4· 2H2O leads to the cationic five-coordinate d6-species [RhH{Si(OH)Ph2}{xant(PiPr2)2}] BArF4 (14) through a silylene intermediate. According to the participation of the latter in the formation of 14, this cation is an efficient catalyst precursor for the monoalcoholysis of diphenylsilane with a wide range of alcohols, reaching turnover frequencies at 50% of conversion between 4000 and 76 500 h-1. The X-ray structures of 3, 6, 7, 9, 12, and 14 are also reported.

Catalytic hydrosilylation of carbonyls via Re(CO)5Cl photolysis

The hydrosilylation reaction between silanes and various carbonyl substrates such as aldehyde, ketone, ester, and carbonate has been catalyzed by Re(CO)5Cl UV photolysis. Kinetic studies have shown that the reaction is favored for the least sterically hindered silanes with aldehydes followed by aliphatic ketones. The IR spectrum of the rhenium carbonyl dimer HRe 2(CO)9(SiR3) has been recorded in the reaction mixture. This complex is believed to be the resting state of the active catalyst Re(CO)4SiR3, which could be released upon photactivation. A catalytic mechanism involving this species has been proposed and shown to be thermodynamically feasible using computational studies. In addition, the relative hydrosilylation rates among the various carbonyl substrates can be explained using the same mechanism.

Reactions of cationic PNP-supported iridium silylene complexes with polar organic substrates

Reactions of PNP-supported silylene complexes [(PNP)(H)Ir-SiRR′] [B(C6F5)4] (R = R′ = Ph (1) and R = H, R′ = Mes (2)) with Lewis bases, carbonyl compounds, alcohols, and amines were investigated. Addition of DMAP (4-dimethylaminopyridine) to 1 and 2 produced base-stabilized silylene complexes [(PNP)(H)IrSiRR′(DMAP)] [B(C6F5)4] (R = R′ = Ph (3) and R = H, R′ = Mes (4)). Reactions of 2 with benzophenone and benzaldehyde afforded the products of stoichiometric hydrosilylation, heteroatom-substituted silylene complexes [(PNP)(H)Ir-SiMes(OCH(Ph)(R))][B(C6F5) 4] (R = Ph (5) and R = H (6)). Complex 1 reacted with DMF or benzophenone, and 2 reacted with DMF, to afford base-stabilized silylene complexes of the type [(PNP)(H)IrSiRR′(B)][B(C6F 5)4] (R = H, R′ = Mes, B = DMF (7); R = R′ = Ph, B = DMF (8) and O-CPh2 (9)). In contrast, treatment of 1 with acetophenone afforded {(PNPH)IrH[SiPh2(OC(-CH2)Ph)]} [B(C6F5)4] (10), from activation of a C-H bond at the α-carbon position of acetophenone. Reactions of alcohols and amines with 1 afforded [(PNPH)IrH(SiPh2OR)][B(C6F 5)4] (R = 3,5-tBu2C 6H3 (11), R = Ph (12), R = iPr (13), and R = tBu (14)) and [(PNPH)IrH(SiPh2NHR)][B(C6F 5)4] (R = Ph (15), R = 3,5-(CF3) 2C6H3 (16)). Exploration of the catalytic activity of iridium silylene complexes with these organic substrates demonstrated that 1 is an effective catalyst for silane alcoholysis and aminolysis and for the hydrosilylation of ketones.

Convenient and selective preparation of mono-alkoxyphenylsilanes from phenylsilane and alcohols

The selective dehydrogenative coupling of phenylsilane and alcohols, including primary, secondary, and tertiary alcohols, was smoothly catalyzed by bis(hexafluoroacetylacetonato)-copper(II) complex to afford the corresponding mono-alkoxysilanes in good-to