22034-20-4

Upstream product

• 149-74-6 dichloromethylphenylsilane 
• 766-08-5 methylphenylsilane 

Downstream Products

• 22034-19-1 deuterio(dimethyl)phenylsilane 
• 18243-13-5 Et₂Si⁽²⁾H₂ 

Relevant academic research and scientific papers

Activation of N-heterocyclic carbenes by {BeH2} and {Be(H)(Me)} fragments

A stable three-coordinate dimethylberyllium species coordinated by the 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes) ligand is readily converted to the corresponding methylhydrido derivative through metathetical reaction with phenylsilane. Attempts to synthesize the corresponding molecular dihydrides are, however, unsuccessful and result in ring opening of an IMes ligand through hydride transfer to the donor carbon atom and the consequent formation of a heterocyclic beryllium organoamide. In agreement with previous calculations, we suggest that this process occurs via a Schlenk-type equilibration process and formation of a four-coordinate bis-NHC beryllium dihydride. These species are not observed, however, as the steric pressure exerted by coordination of the two sterically demanding IMes ligands is sufficient to induce hydride transfer. The latter deduction is supported by the observation that a similar ring-opened product, but derived from methyl and hydride transfer, is available through the introduction of a further equivalent of IMes to the isolated beryllium methyl hydride species. In the latter case the ring-opening process is more facile, which we ascribe to the increased steric pressure achieved upon the formation of four-coordinate beryllium. In a further striking reaction under more forcing thermal conditions, the carbene carbon center of an IMes ligand is observed to be completely eliminated with selective formation of a three-coordinate diamidoberyllium species.

Iron-Catalyzed H/D Exchange of Primary Silanes, Secondary Silanes, and Tertiary Siloxanes

A synthetic study into the catalytic hydrogen/deuterium (H/D) exchange of 1° silanes, 2° silanes, and 3° siloxanes is presented, facilitated by iron-β-diketiminato complexes (1a and 1b). Near-complete H/D exchange is observed for a variety of aryl- and alkyl-containing hydrosilanes and hydrosiloxanes. The reaction tolerates alternative hydride source pinacolborane (HBpin), with quantitative H/D exchange. A synthetic and density functional theory (DFT) investigation suggests that a monomeric iron-deuteride is responsible for the H/D exchange.

Cobalt-Catalyzed Radical Hydroamination of Alkenes with N-Fluorobenzenesulfonimides

An efficient and general radical hydroamination of alkenes using Co(salen) as catalyst, N-fluorobenzenesulfonimide (NFSI) and its analogues as both nitrogen source and oxidant was successfully disclosed. A variety of alkenes, including aliphatic alkenes, styrenes, α, β-unsaturated esters, amides, acids, as well as enones, were all compatible to provide desired amination products. Mechanistic experiments suggest that the reaction underwent a metal-hydride-mediated hydrogen atom transfer (HAT) with alkene, followed by a pivotal catalyst controlled SN2-like pathway between in situ generated organocobalt(IV) species and nitrogen-based nucleophiles. Moreover, by virtue of modified chiral cobalt(II)-salen catalyst, an unprecedented asymmetric version was also achieved with good to excellent level of enantiocontrol. This novel asymmetric radical C?N bond construction opens a new door for the challenging asymmetric radical hydrofunctionalization.

Homoleptic cobalt(II) phenoxyimine complexes for hydrosilylation of aldehydes and ketones without base activation of cobalt(II)

Air-stable, easy to prepare, homoleptic cobalt(II) complexes bearing pendant-modified phenoxyimine ligands were synthesized and determined. The complexes exhibited high catalytic performance for reducing aldehydes and ketones via catalytic hydrosilylation, where a hydrosilane and a catalytic amount of the cobalt(II) complex were added under base-free conditions. The reaction proceeded even in the presence of excess water, and excellent functional-group tolerance was observed. Subsequent hydrolysis gave the alcohol in high yields. Moreover, H2O had a critical role in activation of the Co(II) catalyst with hydrosilane. Several additional results also indicated that the cobalt(II) center acts as an active catalyst in the hydrosilylation of aldehydes and ketones.

Catalytic Access to Bridged Sila- N-heterocycles from Piperidines via Cascade sp3 and sp2 C-Si Bond Formation

Described herein is the development of an unprecedented route to bridged sila-N-heterocycles via B(C6F5)3-catalyzed cascade silylation of N-aryl piperidines with hydrosilanes. Mechanistic studies indicated that an outer-sp

Silane deuteration catalyzed by ruthenium bis(dihydrogen) complexes or simple metal salts

The deuteration of a diverse group of silanes: alkyl-, aryl-, alkoxy- and chlorosilanes, siloxane and silazane, under an atmosphere of dideuterium (D 2) was explored with ruthenium bis(dihydrogen) dihydride complexes and hydrated metal salts. Deuterium incorporation of greater than 97% for the silanes O(SiMe2H)2, Et3SiH, (EtO) 3SiH and Me2ClSiH was possible with 0.1 mol% of the ruthenium complex [RuH2(η2-H2) 2(PCyp3)2] [0.05 mol% for O(SiMe 2H)2] when catalysis was conducted in the neat silane at 30°C under 1 bar of D2 for 3.5 h. The air-stable ruthenium trichloride salt RuCl3xH2O was also an efficient catalyst for the deuteration of O(SiMe2H)2 and Et 3SiH; deuterium incorporations for the two silanes of 93% and 90%, respectively, were possible under the same conditions as for [RuH 2(n2-H2)2(PCyp3) 2] with 0.1% catalyst loading. Hydrogendeuterium exchange of O (SiMe2H)2 catalyzed by the rhodium trichloride (RhCl 3xH2O) and iridium trichloride (IrCl 3xH2O) was similarly efficient as with RuCl 3xH2O although catalytic alacrity dropped for Et 3SiH.

Facile activation of H-H and Si-H bonds by boranes

The borane B(C6F5)3 is a precatalyst for H/Dexchange between H2 and deuterium-labeled silanes (D 3SiPh, D2SiMePh, DSiMe2Ph, DSiEt3). Experimental and DFT studies revea