1333557-75-7Relevant academic research and scientific papers
Si-H Bond Activation with Bullock's Cationic Tungsten(II) Catalyst: CO as Cooperating Ligand
Fuchs, Julien,Irran, Elisabeth,Hrobárik, Peter,Klare, Hendrik F. T.,Oestreich, Martin
supporting information, p. 18845 - 18850 (2019/11/28)
An in-depth investigation of the reaction of tertiary hydrosilanes with [CpW(CO)2(IMes)]+[B(C6F5)4]- reveals a fundamentally new Si-H bond activation mode. Unlike the originally proposed oxidative addition of the Si-H bond to the tungsten(II) center, there is strong experimental and NMR spectroscopic evidence for the involvement of one of the CO ligands of the cationic complex in the Si-H bond breaking event. The Si-H bond is heterolytically cleaved to form a tungsten(II) hydride and a silylium ion, which is stabilized by one of the CO ligands. This reactive hydrosilane adduct was eventually isolated and characterized by X-ray diffraction analysis. Quantum-chemical calculations support a cooperative mechanism, but a stepwise process consisting of oxidative addition and subsequent tungsten-to-oxygen silyl migration in the tungsten(IV) silyl hydride is also energetically feasible. However, our combined spectroscopic and computational analysis favors the cooperative pathway. The newly identified hydrosilane adduct is the key intermediate of Bullock's ionic carbonyl hydrosilylation.
Large-scale preparation and labelling reactions of deuterated silanes
Campos, Jesus,Rubio, Miguel,Esqueda, Ana C.,Carmona, Ernesto
experimental part, p. 29 - 38 (2012/06/30)
A catalytic synthesis of deuterated silanes SiEt3D, SiMe 2PhD and SiPh2D2 is reported that allows their facile generation in a 3-4g scale, utilizing D2 (0.5bar) as the hydrogen isotope source and low
Rhodium-catalyzed, efficient deutero- and tritiosilylation of carbonyl compounds from hydrosilanes and deuterium or tritium
Rubio, Miguel,Campos, Jesuus,Carmona, Ernesto
supporting information; experimental part, p. 5236 - 5239 (2011/12/15)
A cationic rhodium compound which is an active catalyst for both the hydrogen isotope exchange in hydrosilanes and the hydrosilylation of carbonyl compounds permits, in a one-flask, two-step procedure, efficient deutero- and tritiosilylations using SiEt3H under D2 (0.5 bar) or T2, at low catalyst loadings (0.1-0.5 mol %).
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
