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
On the mechanism of metal colloid catalyzed hydrosilylation: proposed explanations for electronic effects and oxygen cocatalysis
作者:Larry N. Lewis
DOI:10.1021/ja00172a014
日期:1990.8
On etudie divers aspects de la reaction d'hydrosilylation, R 3 SiH+R'CH=CH 2 , catalysee par le platine, et un mecanisme base sur des intermediaires colloidaux est propose
在研究的不同方面 de la reaction d'hydrosilylation, R 3 SiH+R'CH=CH 2 , catalysee par le platine, et un mecanisme base sur des intermediaires colloidaux est 提出
Steric Effects in the Catalytic Tandem Isomerization‐Hydrosilylation Reaction
作者:Unai Prieto、Susan Azpeitia、Eider San Sebastian、Zoraida Freixa、María A. Garralda、Miguel A. Huertos
DOI:10.1002/cctc.202001699
日期:2021.3.5
sulfur atom results on a difference in the activity of this tandem reaction. Experimental observations demonstrate that the isomerization process is the rate‐determining step of this catalytic transformation. This process would be of value to the chemical industry because mixtures of internal aliphatic olefins are substantially cheaper and more readily available than the pure terminal isomers.
据报道,由远程烯烃选择性合成线型硅烷。合成了四种新的硅烷-硫醚双齿配体[SiMe 2 H(o- C 6 H 4 SR)](R = i Bu,戊基,苄基,新戊基),并用于形成不饱和和阳离子的16电子氢化硅烷基-铑III复合体。这些化合物是室温下在无溶剂条件下进行串联催化烯烃异构化-氢化硅烷化反应的有效催化剂。硫原子上取代基大小的不同导致了该串联反应活性的差异。实验观察表明,异构化过程是该催化转化的决定速率的步骤。该方法对于化学工业将是有价值的,因为内部脂族烯烃的混合物比纯末端异构体便宜得多并且更容易获得。