15545-80-9Relevant academic research and scientific papers
Scalable Synthesis of Hydrido-Disiloxanes from Silanes: A One-Pot Preparation of 1,3-Diphenyldisiloxane from Phenylsilane
Buonomo, Joseph A.,Eiden, Carter G.,Aldrich, Courtney C.
, p. 278 - 281 (2018)
A simple, one-pot, and high-yielding synthesis of 1,3-diphenyldisiloxane is presented. The preparation of similar symmetrical disiloxane materials is also accomplished with this same protocol. This mechano-chemical procedure is efficient and highly scalab
An efficient and simple method for the preparation of symmetrical disiloxanes from hydrosilanes by Lewis acid-catalyzed air oxidation
Sridhar, Madabhushi,Ramanaiah, Beeram China,Narsaiah, Chinthala,Kumara Swamy, Mudam,Mahesh, Bellam,Kumar Reddy, Mallu Kishore
, p. 7166 - 7168 (2009)
Symmetrical disiloxanes were prepared in high yields by air oxidation of mono, di, and trihydrosilanes under Lewis acid catalysis.
Gold(I) complexes with chloro(diaryl)silyl ligand. Stoichiometric reactions and catalysis for O-functionalization of organosilane
Kanda, Atsushi,Osakada, Kohtaro,Tsuchido, Yoshitaka
supporting information, (2020/03/11)
An Au(I) complex with a chloro(diphenyl)silyl ligand [Au(SiPh2Cl)(PCy3)] (1a) is obtained from the reaction of Ph2SiH2 with [AuCl(PCy3)]. (4-FC6H4)2SiH2, (4-MeC6H4)2SiH2, and Ph2GeH2 react with [AuCl(PCy3)] to form complexes with the chlorodiarylsilyl ligand, [Au(SiAr2Cl)(PCy3)] (1b: Ar = C6H4-4-F, 1c: Ar = C6H4-4-Me) and with the chloro(diphenyl)germyl ligand, [Au(GePh2Cl)(PCy3)] (2a), respectively. Complex 1a reacts with H2O to form Ph2SiH(OH) and (Ph2SiH)2O, whereas the reaction of EtOH with 1a yields Ph2SiH(OEt) exclusively. Complex 1a catalyzes the hydrolysis of Ph2SiH2 ([Au]:[H2SiPh2]:[H2O] = 0.05:1.0:10.0) at 60 °C to yield Ph2SiH(OH) and (Ph2SiH)2O. The reaction of Ph2SiH2 with HOEt in the presence of a catalytic amount of 1a affords Ph2SiH(OEt). Both stoichiometric and catalytic reactions using 1a lead to the recovery of [AuCl(PCy3)] from the reaction mixture.
First study of rhodium(I) complexes with chiral sulfur-containing terpenoids as catalytic systems for ketone hydrosilylation
Uvarov, Vladimir M.,de Vekki, Dimitry A.
, p. 376 - 387 (2019/12/24)
Using a “chiral pool” approach, a number of chiral thiolate and sulfide ligands based on natural terpenes and terpenoids have been synthesized in a few simple steps. Two new Rh-thiolate complexes with the formula [Rh(CO)2(μ-SR)]2 were obtained. The influence of these complexes and catalytic systems formed by combining the synthesized ligands with [Rh(CO)2(μ-Cl)]2 and [Rh(cod)(μ-Cl)]2, on the reaction rate, chemoselectivity, stereoselectivity and formation of tetraphenyldisiloxane in Rh-catalyzed asymmetric hydrosilylation of acetophenone as a model reaction have been studied. Mechanistic aspects of formation of silyl enol ether as a side product in the presence of S-containing ligands are presented.
Catalytic oxidation of diorganosilanes to 1,1,3,3-tetraorganodisiloxanes with gold nanoparticle assembly at the water-chloroform interface
Shankar, Ravi,Sharma, Asmita,Jangir, Bhawana,Chaudhary, Manchal,Kociok-K?hn, Gabriele
, p. 813 - 819 (2019/01/09)
The formation of the spherical self-assembly of gold nanoparticles (AuNPs) of 200 ± 20 nm size at the water-chloroform interface is achieved by employing the cyclotetrasiloxane [RSCH2CH2SiMeO]4 (R = CH2CH2OH) as the stabilizing ligand. The interfacially stabilized AuNPs act as a versatile catalyst for selective hydrolytic oxidation of only one of the Si-H bonds in secondary organosilanes, RR1SiH2 (R, R1 = alkyl, aryl, and sila-alkyl), to afford the high yield synthesis of 1,1,3,3-tetraorganodisiloxanes, (HRR1Si)2O. The study unravels for the first time the role of the photothermal effect arising from the excitation of the surface plasmon resonance of the AuNPs under visible light irradiation in enhancing the catalytic activity at ambient temperature.
A novel synthetic approach to poly(hydrosiloxane)s via hydrolytic oxidation of primary organosilanes with a AuNPs-stabilized Pickering interfacial catalyst
Shankar, Ravi,Jangir, Bhawana,Sharma, Asmita
, p. 344 - 351 (2017/01/13)
The triblock copolymer, PiBA20-b-PDMS75-b-PiBA20 (PiBA = polyisobornylacrylate, PDMS = polydimethylsiloxane), 1 is employed as an amphiphilic scaffold for surface functionalization of AuNPs of 10-15 nm size in chloroform.
Ligand-controlled, norbornene-mediated, regio- and diastereoselective rhodium-catalyzed intramolecular alkene hydrosilylation reactions
Hua, Yuanda,Nguyen, Hiep H.,Scaggs, William R.,Jeon, Junha
supporting information, p. 3412 - 3415 (2013/07/26)
Ligand-controlled, norbornene-mediated, regio- and diastereoselective rhodium-catalyzed intramolecular alkene hydrosilylation of homoallyl silyl ethers (1) exploiting either BINAP or 1,6-bis(diphenylphosphino)hexane (dpph) has been developed. This method
Kinetics and mechanisms of the reactions of transient silylenes with amines
Kostina, Svetlana S.,Singh, Tishaan,Leigh, William J.
experimental part, p. 937 - 946 (2012/01/13)
The N-H insertion reactions of dimethyl-, diphenyl-, and dimesitylsilylene (SiMe2, SiPh2, and SiMes2, respectively) with n-butylamine (BuNH2) and diethylamine (Et2NH) were studied in hexanes by steady-state and laser photolysis methods. The process begins with the formation of the corresponding Lewis acid-base complexes, which decayed with second-order kinetics at rates that show modest sensitivity to silylene and amine structures. The complexation process, which was also studied using triethylamine (Et3N), proceeds at rates close to the diffusion limit, but the rate constants vary systematically with steric bulk in the amine. Equilibrium constants were determined for the complexation of Et2NH and Et3N with SiMes2, which proceeds reversibly. The complexes of SiMe2 and SiPh2 with BuNH2 and Et2NH decayed with pseudo-first-order rate coefficients in the 104-105s-1 range. This is consistent with upper limits of about 106M-1s-1 for the rate constants for amine-catalyzed H-migration, which is thought to be the dominant mechanism for product formation from the complexes. The results are compared to published kinetic data for the O-H insertion reactions of these silylenes with alcohols, which also proceeds via initial complexation followed by catalytic proton transfer. The results indicate that catalyzed H-transfer in the amine complexes is at least 104 times slower than the analogous process in silylene-MeOH complexes. The experimental data are compared to the results of theoretical calculations of the SiMe2+NH2Me and SiMe 2+MeOH potential energy surfaces, carried out at the Gaussian-4 and B3LYP/6-311+G(d,p) levels of theory.
Reactions of (Et2NCH2CH2NEt 2)·H2SiCl2 with selected diorganometallic reagents of magnesium and lithium
Corey, Joyce Y.,Trankler, Kevin A.,Braddock-Wilking, Janet,Rath, Nigam P.
experimental part, p. 5708 - 5713 (2011/02/16)
Addition of the THF-insoluble di-Grignard reagent from 2,2′-dibromo- 4,4′-tert-butylbiphenyl (1) to a solution of [(teeda)·H 2SiCl2] in CH2Cl2/THF produced 2,7-di-tert-butyl-9H-9-silafluorene (3) in isolated, recrystallized yields of 2O, when reacted with [(teeda)·H2SiCl2] in CH2Cl 2/Et2O, gave similar yields of 5,10-dihydro-2,5,8- trimethylphenazasiline (4). In the absence of CH2Cl2 the major product produced from 1 was the spirocycle 2,2′,7,7′-tetra- tert-butyl-9,9′-spirobi[9H-9-silafluorene] both in a solvent-free form (5′) and as an ethanol solvate (5), both of which were crystallographically characterized. The spirocycle 2,2′,5,5′,8, 8′-hexamethyl-5,10-dihydro-10,10-spirobiphenazasiline (6) was formed from the reaction of the dilithio reagent of 2 in the absence of CH 2Cl2.
Hydrosilylation of acetophenone with diphenylsilane in the presence of rhodium(I) complexes with chiral amines
Uvarov,De Vekki,Reshetilovskii,Skvortsov
body text, p. 35 - 46 (2010/05/01)
New chiral rhodium complexes cis-[Rh(CO)2(RNH2)Cl] [RNH2 = (R)-(-)-cis-MyrtNH2, (R)-(-)-MenthylNH 2, (R)-(+)-BornylNH2] were synthesized and their catalytic properties in reactions of hydrosilylation of acetophenone with diphenylsilane were studied. It was shown that the reaction products were diphenyl-1- phenylethoxysilane, diphenyl-1-phenylvinyloxysilane and 1,1,3,3- tetraphenyldisiloxane. The best catalytic activity displayed (-)-cis-[Rh(CO)2(MenthNH2)Cl]. The hydrosilylation of acetophenone with diphenylsilane in the presence of [Rh(CO)2(μ-Cl) ]2 and [Rh(cod)Cl]2 and amines in situ was studied. The best ratio amine:complex = 5:1 was established. With the catalytic systems based on [Rh(cod)Cl]2 or [Rh(CO)2(μ-Cl)]2 the activity increased in the series of amines: (R)-(-)-cis-MyrtNH2 2 2, and (R)-(-)-MenthylNH2 2 2, respectively. The chemoselectivity maximum was observed in the presence of [Rh(cod)Cl]2 with (R)-(-)-MenthylNH 2 and [Rh (CO)2(μ-Cl)]2 with (R)-(+)-BornylNH2; maximum asymmetric induction was 43.5% ee at the use of [Rh(CO)2 (μ-Cl)]2 and (R)-(+)-BornylNH 2.
