18536-60-2Relevant academic research and scientific papers
Silane deuteration catalyzed by ruthenium bis(dihydrogen) complexes or simple metal salts
Smart, Katharine A.,Mothes-Martin, Emmanuelle,Annaka, Tatsuro,Grellier, Mary,Sabo-Etienne, Sylviane
, p. 759 - 764 (2014)
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.
Activation of Si-H bonds across the nickel carbene bond in electron rich nickel PCcarbeneP pincer complexes
LaPierre, Etienne A.,Piers, Warren E.,Spasyuk, Denis M.,Bi, David W.
, p. 1361 - 1364 (2016)
Silicon-hydrogen bonds are shown to add to a nickel carbon double bond to yield nickel α-silylalkyl hydrido complexes. Kinetic and isotope labeling studies suggest that a concerted 4-centred addition across the NiC bond is operative rather than a mechanism involving Si-H oxidative addition. This constitutes an example of Si-H bond activation via ligand cooperativity.
A General Rhodium Catalyst for the Deuteration of Boranes and Hydrides of the Group 14 Elements
Esteruelas, Miguel A.,Martínez, Antonio,Oliván, Montserrat,Vélez, Andrea
, p. 15693 - 15698 (2020)
Pinacolborane, catecholborane, triethylsilane, triphenylsilane, dimethylphenylsilane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, triethylgermane, triphenylgermane, and triphenylstannane deuterated at the heteroatom position have been catalytically prepared in
Potassium-Catalyzed Hydrosilylation of Activated Olefins: Evidence for a Silyl Migration Mechanism
Leich, Valeri,Spaniol, Thomas P.,Okuda, Jun
, p. 1179 - 1182 (2016)
The alkali-metal silyl [K(L)SiPh3] (1; L = 18-crown-6 ether) catalyzed the hydrosilylation of activated C=C double bonds. Isolation and characterization of an addition product is in agreement with the anti-Markovnikov selectivity. Second-order
Carbanion mechanisms XX. Is there charge delocalization in phenyl-substituted Group 4 anions? Evidence from electronic absorption spectroscopy
Buncel, Erwin,Gordon, Robert D.,Venkatachalam, T. Krishnan
, p. 81 - 83 (1996)
From the electronic absorption spectra of the triphenyl silyl, germyl, stannyl and plumbyl anions Ph3E- (E = Si, Ge, Sn or Pb), it is concluded that there exists in these species almost no conjugation between the Group 4 element and the phenyl group substituents, contrasting with the Ph3C- carbanion. A similar conclusion can be drawn from the near constancy of λmax values in the series Ph3Si-, Ph2SiH- and PhSiH-2.
Visible-light-mediated deuteration of silanes with deuterium oxide
Zhou, Rong,Li, Jiesheng,Cheo, Han Wen,Chua, Rachel,Zhan, Gu,Hou, Zhaomin,Wu, Jie
, p. 7340 - 7344 (2019/08/20)
Isotopically labeled compounds are highly desirable as they can serve as both mechanistic probes in chemistry and diagnostic tools in medicinal research. Herein, we report an unprecedented visible-light-mediated metal-free deuteration of silanes using Ds
A Free Radical Cascade Silylarylation of Activated Alkenes: Highly Selective Activation of the Si-H/C-H Bonds
Zhang, Lizhi,Liu, Dong,Liu, Zhong-Quan
, p. 2534 - 2537 (2015/06/02)
The first example of silylarylation of activated alkenes with silanes is reported via selective activation of the Si-H/C-H bonds, which allows efficient access to silylated oxindoles through a free-radical cascade process. (Chemical Equation Presented).
Synthesis and reactivity of new bis(N-heterocyclic carbene) iridium(I) complexes
Nelson, David J.,Truscott, Byron J.,Slawin, Alexandra M. Z.,Nolan, Steven P.
supporting information, p. 12674 - 12681 (2013/11/19)
New complexes of the type trans-[IrCl(η2-COE)(NHC) 2] (COE = cis-cyclooctene; NHC = N-heterocyclic carbene) have been prepared in one step from the reaction of ca. 4 equiv of NHC or [AgCl(NHC)] with [IrCl(η2-COE)2/su
Catalytic deuteration of silanes mediated by N-heterocyclic carbene-Ir(iii) complexes
Fortman, George C.,Jacobsen, Heiko,Cavallo, Luigi,Nolan, Steven P.
supporting information; experimental part, p. 9723 - 9725 (2011/10/05)
The catalytic activity of a series of coordinatively unsaturated NHC-M(iii) (M = Rh, Ir; NHC = N-heterocyclic carbene) complexes was tested in the deuteration of secondary and tertiary silanes. Among these, [IrCl(I tBu′)2] provides t
A cationic Rh(III) complex that efficiently catalyzes hydrogen isotope exchange in hydrosilanes
Campos, Jesus,Esqueda, Ana C.,Lopez-Serrano, Joaquin,Sanchez, Luis,Cossio, Fernando P.,De Cozar, Abel,Alvarez, Eleuterio,Maya, Celia,Carmona, Ernesto
supporting information; experimental part, p. 16765 - 16767 (2011/02/16)
The synthesis and structural characterization of a mixed-sandwich (η5-C5Me5)Rh(III) complex of the cyclometalated phosphine PMeXyl2 (Xyl = 2,6-C6H 3Me2) with unusual κ4/sup
