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Upstream product

• 119-61-9 benzophenone 
• 775-12-2 diphenylsilane 
• 91-01-0 1,1-Diphenylmethanol 
• 1631-83-0 diphenylsilyl chloride 

Downstream Products

• 91-01-0 1,1-Diphenylmethanol 

Relevant academic research and scientific papers

Trivalent Rare-Earth Metal Amide Complexes as Catalysts for the Hydrosilylation of Benzophenone Derivatives with HN(SiHMe2)2 by Amine-Exchange Reaction

The rare-earth metal complexes Ln(L1)[N(SiHMe2)2](thf) (Ln=La, Ce, Y; L1=N,N′′-bis(pentafluorophenyl)diethylenetriamine dianion) were synthesized by treating Ln[N(SiHMe2)2]3(thf)2 with L1H2. The lanthanum and cerium derivatives are active catalysts for the hydrosilylation of benzophenone derivatives with HN(SiHMe2)2. An amine-exchange reaction was revealed as a key step of the catalytic cycle, in which Ln?Si?H β-agostic interactions are proposed to promote insertion of the carbonyl moiety into the Si?H bond.

Hypercoordinate ketone adducts of electrophilic π3-H2SiRR′ ligands on ruthenium as key intermediates for efficient and robust catalytic hydrosilation

The electrophilic π3-H2SiRR′ σ-complexes [PhBPPh3]RuH(π3-H2SiRR′) (RR′ = MePh, 1a; Ph2, 1b; [PhBPPh3]- = [PhB(CH2PPh2)

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Bismuth compounds are gaining importance as potential alternatives to transition-metal complexes and electron deficient lighter p-block compounds in homogeneous catalysis. Computational analysis on the two-coordinate [(Me2NC6H4)Bi]2+ possessing three electrophilic sites is experimentally evidenced by the isolation of [{Me2NC6H4}Bi{OP(NMe2)3}3][B(3,5-C6H3Cl2)4]2. These observations led us to generate dicationic organobismuth catalyst, [(Me2NC6H4)Bi(L)3]2+ (L=aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single-crystal X-ray diffraction in the solid state. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support a carbonyl activation mechanism at the bismuth center followed by Si?H addition.

Structural Elucidation of Silver(I) Amides and Their Application as Catalysts in the Hydrosilylation and Hydroboration of Carbonyls

This study details the isolation and characterisation of three novel silver(I) amides in solution and solid-state, [Ag(Cy3P)(HMDS)] 2, [Ag(Cy3P){N(TMS)(Dipp)}] 3 and [Ag(Cy3P)2(NPh2)] 4. Their catalytic abilities have proved successful in hydroboration and hydrosilylation reactions with a full investigation performed with complex 2. Both protocols proceed under mild conditions, displaying exceptional functional-group tolerance and chemoselectivity, in excellent conversions at competitive reaction times. This work reveals the first catalytic hydroboration of aldehydes and ketones performed by a silver(I) catalyst.

E-H Bond Activations and Hydrosilylation Catalysis with Iron and Cobalt Metalloboranes

An exciting challenge in transition metal catalyst design is to explore whether earth-abundant base metals such as Fe, Co, and Ni can mediate two-electron reductive transformations that their precious metal counterparts (e.g., Ru, Rh, Ir, and Pd) are better known to catalyze. Organometallic metalloboranes are an interesting design concept in this regard because they can serve as organometallic frustrated Lewis pairs. To build on prior studies with nickel metalloboranes featuring the DPB and PhDPBMes ligands in the context of H2 and silane activation and catalysis (DPB = bis(o-diisopropylphosphinophenyl)phenylborane, PhDPBMes = bis(o-diphenylphosphinophenyl)mesitylborane), we now explore the reactivity of iron, [(DPB)Fe]2(N2), 1, and cobalt, (DPB)Co(N2), 2, metalloboranes toward a series of substrates with E-H bonds (E = O, S, C, N) including phenol, thiophenol, benzo[h]quinoline, and 8-aminoquinoline. In addition to displaying high stoichiometric E-H bond activation reactivity, complexes 1 and 2 prove to be more active catalysts for the hydrosilylation of ketones and aldehydes with diphenylsilane relative to (PhDPBMes)Ni. Indeed, 2 appears to be the most active homogeneous cobalt catalyst reported to date for the hydrosilylation of acetophenone under the conditions studied.

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.

Iron-Catalyzed Hydrosilylation of Aldehydes and Ketones under Solvent-Free Conditions

Exposure of aldehyde or ketone to 1 mol % BIAN-Fe(C7H8) complex in the presence of diphenyl silane affords the corresponding protected alcohol in excellent yields, under mild reaction conditions. Aldehydes and ketones are reduced cleanly in the presence of a broad range of functional groups under solvent-free conditions.

A remarkably active iron catecholate catalyst immobilized in a porous organic Polymer

A single-site, iron catecholate-containing porous organic polymer was prepared and utilized as a stable and remarkably active catalyst for the hydrosilylation of ketones and aldehydes. In some instances, catalyst loadings of 0.043-2.1 mol % [Fe] were sufficient for complete hydrosilylation of aldehydes and ketones within 15 min at room temperature. The catalyst can be recycled at least three times without a drop in catalytic activity. This system is an example of an immobilized homogeneous catalyst with no homogeneous analogue.

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.

Direct reduction of alcohols: Highly chemoselective reducing system for secondary or tertiary alcohols using chlorodiphenylsilane with a catalytic amount of indium trichloride

The direct reduction of alcohols using chlorodiphenylsilane as A hydride source in the presence of a catalytic amount of indium trichloride is described. Benzylic alcohols, secondary alcohols, and tertiary alcohols were effectively reduced to give the corresponding alkanes in high yields. A compound bearing both primary and secondary hydroxyl groups was reduced only at the secondary site to afford the primary alcohol after workup with Bu4NF. This system showed high chemoselectivity only for the hydroxyl group while not reducing other functional groups that are readily reduced by standard reducing systems. Thus alcohols bearing ester, chloro, bromo, or nitro groups, which are sensitive to LiAlH4 or Zn/H+, were selectively reduced only at the hydroxyl sites by the chlorodiphenylsilane/InCl3 system. NMR studies revealed the reaction course. The hydrodiphenyl-silyl ether is initially formed and then, with InCl3 acting as a Lewis acid, forms an oxonium complex, which accelerates the desiloxylation with donation of the hydrogen to the carbon.