Carbonyl and olefin hydrosilylation mediated by an air-stable phosphorus(<scp>iii</scp>) dication under mild conditions
作者:Ryan J. Andrews、Saurabh S. Chitnis、Douglas W. Stephan
DOI:10.1039/c9cc02460c
日期:——
The readily-accessible, air-stable Lewis acid [(terpy)PPh][B(C6F5)4]21 is shown to mediate the hydrosilylation of aldehydes, ketones, and olefins. The utility and mechanism of these hydrosilylations are considered.
已显示出易于获得的,空气稳定的路易斯酸[(terpy)PPh] [B(C 6 F 5)4 ] 2 1可介导醛,酮和烯烃的氢化硅烷化。考虑了这些氢甲硅烷基化的效用和机理。
The Highly Lewis Acidic Dicationic Phosphonium Salt: [(SIMes)PFPh
<sub>2</sub>
][B(C
<sub>6</sub>
F
<sub>5</sub>
)
<sub>4</sub>
]
<sub>2</sub>
作者:Michael H. Holthausen、Meera Mehta、Douglas W. Stephan
DOI:10.1002/anie.201403693
日期:2014.6.16
The dicationic imidazolium‐phosphoniumsalt [(SIMes)PFPh2][B(C6F5)4]2 has been prepared and shown to exhibit remarkable Lewis acidity in stoichiometric reactions and acting as an effective Lewisacid catalyst for the hydrodefluorination of fluoroalkanes and the hydrosilylation of olefins.
制备了咪唑鎓‐盐[(SIMes)PFPh 2 ] [B(C 6 F 5)4 ] 2,在化学计量反应中显示出显着的路易斯酸性,可作为有效的路易斯酸催化剂用于氟代烷烃的加氢脱氟和烯烃的氢化硅烷化。
From Remote Alkenes to Linear Silanes or Allylsilanes depending on the Metal Center
作者:Susan Azpeitia、Antonio Rodriguez-Dieguez、María A. Garralda、Miguel A. Huertos
DOI:10.1002/cctc.201800159
日期:2018.5.24
allylsilanes from remote alkenes was explored. The cationic, unsaturated, 16‐electron hydrido–silyl–RhIII complex was found to be an efficient catalyst for a tandem catalytic alkene isomerization–hydrosilylation reaction at room temperature under solvent‐free conditions. The analogous hydrido–silyl–IrIII complex was selective for dehydrogenativesilylation, which led to the formation of terminal allylsilanes.
Rhodium(III) Catalyzed Solvent-Free Tandem Isomerization-Hydrosilylation From Internal Alkenes to Linear Silanes
作者:Susan Azpeitia、María A. Garralda、Miguel A. Huertos
DOI:10.1002/cctc.201700222
日期:2017.6.8
The selective synthesis of linear silanes from internal alkenes or alkene mixtures is reported. Unsaturated 16 electrons hydrido–silyl–RhIII complexes are efficient catalysts for a tandem catalytic alkene isomerization–hydrosilylation reaction at room temperature under solvent‐free conditions. Such a process would be of value to the chemical industry, as mixtures of internal aliphatic olefins are substantially