3439-16-5Relevant articles and documents
Synthesis, spectroscopic characterization and catalytic activity of platinum(II) carbene complexes
Bolbat, Ekaterina,Suarez-Alcantara, Karina,Canton, Sophie E.,Wendt, Ola F.
, p. 129 - 133 (2016)
A novel platinum complex with 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidenyl ligand has been synthesized and characterized on the basis of elemental analysis, MS, 1H and 13C NMR spectroscopy, X-ray Absorption Spect
Accelerated Anti-Markovnikov Alkene Hydrosilylation with Humic-Acid-Supported Electron-Deficient Platinum Single Atoms
Antonietti, Markus,Badamdorj, Bolortuya,Janik, Michael J.,Liu, Kairui,Yang, Fan
supporting information, p. 24220 - 24226 (2021/10/07)
The hydrosilylation reaction is one of the largest-scale applications of homogeneous catalysis, and Pt homogeneous catalysts have been widely used in this reaction for the commercial manufacture of silicon products. However, homogeneous Pt catalysts result in considerable problems, such as undesired side reactions, unacceptable catalyst residues and disposable platinum consumption. Here, we synthesized electron-deficient Pt single atoms supported on humic matter (Pt1@AHA_U_400), and the catalyst was used in hydrosilylation reactions, which showed super activity (turnover frequency as high as 3.0×107 h?1) and selectivity (>99 %). Density functional theory calculations reveal that the high performance of the catalyst results from the atomic dispersion of Pt and the electron deficiency of the Pt1 atoms, which is different from conventional Pt nanoscale catalysts. Excellent performance is maintained during recycle experiments, indicating the high stability of the catalyst.
14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes
Abeynayake, Niroshani S.,Donnadieu, Bruno,Gorla, Saidulu,Montiel-Palma, Virginia,Mu?oz-Hernández, Miguel A.,Zamora-Moreno, Julio
supporting information, p. 11783 - 11792 (2021/09/06)
Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh(iii) devoid of agostic interactions. The complexes [X-Rh(κ3(P,Si,Si)PhP(o-C6H4CH2SiiPr2)2], where X = Cl (Rh-1), Br (Rh-2), I (Rh-3), OTf (Rh-4), Cl·GaCl3(Rh-5); derive from a bis(silyl)-o-tolylphosphine with isopropyl substituents on the Si atoms. All five complexes display a sawhorse geometry around Rh and exhibit similar spectroscopic and structural properties. The catalytic activity of these complexes and [Cl-Ir(κ3(P,Si,Si)PhP(o-C6H4CH2SiiPr2)2],Ir-1, in styrene and aliphatic alkene functionalizations with hydrosilanes is disclosed. We show thatRh-1catalyzes effectively the dehydrogenative silylation of styrene with Et3SiH in toluene while it leads to hydrosilylation products in acetonitrile.Rh-1is an excellent catalyst in the sequential isomerization/hydrosilylation of terminal and remote aliphatic alkenes with Et3SiH including hexene isomers, leading efficiently and selectively to the terminal anti-Markonikov hydrosilylation product in all cases. With aliphatic alkenes, no hydrogenation products are observed. Conversely, catalysis of the same hexene isomers byIr-1renders allyl silanes, the tandem isomerization/dehydrogenative silylation products. A mechanistic proposal is made to explain the catalysis with these M(iii) complexes.
