5931-21-5

Upstream product

• 775-12-2 diphenylsilane 
• 62-53-3 aniline 

Relevant academic research and scientific papers

AreneCr(CO)2(η2-HSiHPh2) Complexes as Catalysts for the Si-H Bond Activation. Hydrolysis of the Si-H Bond and Dehydrogenative Coupling between Diphenylsilane and Nucleophiles

The use of areneCr(CO)2(η2-HSiHPh2) complexes for the efficient catalysis of Si-H bond hydrolysis and, in general, the dehydrogenative coupling of diphenylsilane with nucleophiles is reported; this is the first example of a group VI transition-

Seeking Heteroatom-Rich Compounds: Synthetic and Mechanistic Studies into Iron Catalyzed Dehydrocoupling of Silanes

A detailed synthetic investigation into the dehydrocoupling of silanes with amines, phosphines, and alcohols using an iron precatalyst (1) is presented. We have furnished over 30 examples of aminosilane synthesis along with kinetic studies using MeBnNH and MePhSiH2 as coupling partners. The kinetic studies suggest a reversible reaction with silane which generates aminosilane and an Fe-hydride dimer that undergoes rate-limiting protonolysis with amine with N-H bond cleavage in the transition state, consistent with a primary KIE of 2.42(3). The presence of dimers as on-cycle intermediates was analyzed in depth. Beyond this we have explored the substrate scope of phosphinosilane formation which shows a preferential heterodehydrocoupling to give the phosphinosilane with primary and secondary silanes. Silylethers can also be prepared and alcohols that contain alkene functionality do not show any tendency to reduce the double bond.

Syntheses of Dianionic α-Iminopyridine Rare-Earth Metal Complexes and Their Catalytic Acitivities toward Dehydrogenative Coupling of Amines with Hydrosilanes

Reactions of [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 with aminomethylene-substituted pyridine 2-[O(CH2CH2)2NCH2CH2NCH2]C5H4N (1) gave the dianionic α-iminopyridine rare-earth metal amido complexes {μ-η2:σ1:κ1:κ1-2-[O(CH2CH2)2NCH2CH2NCH]C5H4N}2RE2[N(SiMe3)2]2 (RE = Y(2a), La(2b), Pr(2c), Nd(2d), Sm(2e), Dy(2f), Er(2g), and Lu (2h)). However, reaction of [(Me3Si)2N]3Y(μ-Cl)Li(THF)3 with pyridin-2-ylmethyl-substituted amines such as 2-(RNHCH2)C5H4N (R = tBu (3a) and 2,6-iPr2Ph (3b)) or benzyl-substituted amine O(CH2CH2)2NCH2CH2NHCH2C6H5 (5) afforded the corresponding yttrium complexes containing monoanionic ligands [2-(RNCH2)C5H4N]2YN(SiMe3)2 (R = tBu (4a) and 2,6-iPr2Ph (4b)) or [O(CH2CH2)2NCH2CH2NCH2C6H5][(Me3Si)2N)]Y(μ-Cl)(μ-η3-O(CH2CH2)2NCH2CH2NCH2C6H5)Li(THF) (6). Dianionic α-iminopyridine rare-earth metal amido complexes showed high catalytic activities for the dehydrogenation coupling reaction of hydrosilanes and amines providing a variety of silylamines in high yields.

Si-N Heterodehydrocoupling with a Lanthanide Compound

[La{N(SiMe3)2}3THF2] (1) is an effective precatalyst for the heterodehydrocoupling of silanes and amines. Coupling of primary and secondary amines with aryl silanes was achieved with a loading of 0.8 mol % of [L

Alkaline-Earth-Catalysed Cross-Dehydrocoupling of Amines and Hydrosilanes: Reactivity Trends, Scope and Mechanism

Alkaline-earth (Ae=Ca, Sr, Ba) complexes are shown to catalyse the chemoselective cross-dehydrocoupling (CDC) of amines and hydrosilanes. Key trends were delineated in the benchmark couplings of Ph3SiH with pyrrolidine or tBuNH2. Ae{

Highly efficient dehydrogenative coupling of hydrosilanes with amines or amides using supported gold nanoparticles

Hydroxyapatite-supported gold nanoparticles (Au/HAP) can act as a highly active and reusable catalyst for the coupling of hydrosilanes with amines under mild conditions. Various silylamines can be selectively obtained from diverse combinations of equimola

Catalytic dehydrogenative Si-N coupling of pyrroles, indoles, carbazoles as well as anilines with hydrosilanes without added base

A base-free, catalytic protocol for the dehydrogenative Si-N coupling of weakly nucleophilic N-H groups of heteroarenes or aryl-substituted amines with equimolar amounts of hydrosilanes is reported. Cooperative Si-H bond activation at a Ru-S bond generates a silicon electrophile that forms a Si-N bond prior to the N-H deprotonation by an intermediate Ru-H complex, only releasing H 2. The Royal Society of Chemistry 2013.

Ruthenium carbonyl-catalysed Si-heteroatom X coupling (X = S, O, N)

Ru3(CO)12 has been shown to catalyse the coupling of silanes with thiols, alcohols and amines with turnover number (TON) and turnover frequency (TOF) of up to 200 and 50 h-1 at 80 °C. IR, NMR and mass spectroscopic studies have identified a ruthenium dimer complex, [Ru(CO)4(SiEt3)]2 as a likely resting state of the catalyst. A mechanism involving this complex has been proposed for the silicon-thiol coupling process.

Tris(oxazolinyl)boratomagnesium-catalyzed cross-dehydrocoupling of organosilanes with amines, hydrazine, and ammonia

We report magnesium-catalyzed cross-dehydrocoupling of Si-H and N-H bonds to give Si-N bonds and H2. A number of silazanes are accessible using this method, as well as silylamines from NH3 and silylhydrazines from N2H4. Kinetic studies of the overall catalytic cycle and a stoichiometric Si-N bond-forming reaction suggest nucleophilic attack by a magnesium amide as the turnover-limiting step.

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.