18834-17-8Relevant articles and documents
Ring-Shaped Phosphinoamido-Magnesium-Hydride Complexes: Syntheses, Structures, Reactivity, and Catalysis
Fohlmeister, Lea,Stasch, Andreas
, p. 10235 - 10246 (2016)
A series of magnesium(II) complexes bearing the sterically demanding phosphinoamide ligand, L?=Ph2PNDip?, Dip=2,6-diisopropylphenyl, including heteroleptic magnesium alkyl and hydride complexes are described. The ligand ge
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 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.
