66774-56-9Relevant academic research and scientific papers
Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation
Kannan, Ramkumar,Balasubramaniam, Selvakumar,Kumar, Sandeep,Chambenahalli, Raju,Jemmis, Eluvathingal D.,Venugopal, Ajay
supporting information, p. 12717 - 12721 (2020/09/09)
Bismuth compounds are gaining importance as potential alternatives to transition-metal complexes and electron deficient lighter p-block compounds in homogeneous catalysis. Computational analysis on the two-coordinate [(Me2NC6H4)Bi]2+ possessing three electrophilic sites is experimentally evidenced by the isolation of [{Me2NC6H4}Bi{OP(NMe2)3}3][B(3,5-C6H3Cl2)4]2. These observations led us to generate dicationic organobismuth catalyst, [(Me2NC6H4)Bi(L)3]2+ (L=aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single-crystal X-ray diffraction in the solid state. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support a carbonyl activation mechanism at the bismuth center followed by Si?H addition.
Hydrosilylation of Ketones Catalyzed by Iron Iminobipyridine Complexes and Accelerated by Lewis Bases
Kobayashi, Katsuaki,Izumori, Yosuke,Taguchi, Daisuke,Nakazawa, Hiroshi
, p. 1094 - 1102 (2019/09/06)
Fe-iminobipyridine complexes ((RBPIAr,R′)FeBr2, RBPIAr,R′=iminobipyridine derivatives) were found to exhibit good catalytic activity for hydrosilylation of ketones. The highest TOF (turnover frequency
Hydrosilylation of Aldehydes and Ketones Catalyzed by a Terminal Zinc Hydride Complex, [κ3-Tptm]ZnH
Sattler, Wesley,Ruccolo, Serge,Rostami Chaijan, Mahnaz,Nasr Allah, Tawfiq,Parkin, Gerard
, p. 4717 - 4731 (2015/10/28)
Tris(2-pyridylthio)methyl zinc hydride, [κ3-Tptm]ZnH, is an effective catalyst for multiple insertions of carbonyl groups into the Si-H bonds of PhxSiH4-x (x = 1, 2). Specifically, [κ3-Tptm]ZnH catalyzes the insertion of a variety of aldehydes and ketones into the Si-H bonds of PhSiH3 and Ph2SiH2 to afford PhSi[OCH(R)R′]3 and Ph2Si[OCH(R)R′]2, respectively. The mechanism for hydrosilylation is proposed to involve insertion of the carbonyl group into the Zn-H bond to afford an alkoxy species, followed by metathesis with the silane to release the alkoxysilane and regenerate the zinc hydride catalyst. Multiple insertion of prochiral ketones results in the formation of diastereomeric mixtures of alkoxysilanes that can be identified by NMR spectroscopy.
A remarkably active iron catecholate catalyst immobilized in a porous organic Polymer
Kraft, Steven J.,Sanchez, Raul Hernandez,Hock, Adam S.
, p. 826 - 830 (2013/07/25)
A single-site, iron catecholate-containing porous organic polymer was prepared and utilized as a stable and remarkably active catalyst for the hydrosilylation of ketones and aldehydes. In some instances, catalyst loadings of 0.043-2.1 mol % [Fe] were sufficient for complete hydrosilylation of aldehydes and ketones within 15 min at room temperature. The catalyst can be recycled at least three times without a drop in catalytic activity. This system is an example of an immobilized homogeneous catalyst with no homogeneous analogue.
