Catalysis by cationic oxorhenium(v): hydrolysis and alcoholysis of organic silanes
作者:Rex A. Corbin、Elon A. Ison、Mahdi M. Abu-Omar
DOI:10.1039/b822783g
日期:——
The cationic [2-(2'-hydroxyphenyl)-2-oxazolinato(-2)]oxorhenium(v) complex promotes oxidative dehydrogenation of organosilanes with water and alcohols in a catalytic manner to give excellent yields of silanols and silyl ethers, respectively. The reactions proceed conveniently under ambient and open-flask conditions with low catalyst loading (
Nonclassical Ruthenium Silyl Dihydride Complexes TpRu(PPh
<sub>3</sub>
)(η
<sup>3</sup>
‐HSiR
<sub>3</sub>
H) [Tp = Hydridotris(pyrazolyl)borate]: Catalytic Hydrolytic Oxidation of Organosilanes to Silanols with TpRu(PPh
<sub>3</sub>
)(η
<sup>3</sup>
‐HSiR
<sub>3</sub>
H)
作者:Ting Yan Lee、Li Dang、Zhongyuan Zhou、Chi Hung Yeung、Zhenyang Lin、Chak Po Lau
DOI:10.1002/ejic.201000951
日期:2010.12
appropriate to describe the complexes TpRu(PPh 3 )"H 2 SiR 3 " as TpRu(PPh 3 )(η 3 -HSiR 3 H), a static structure containing H···Si···H bonding rather than a highly fluxional pair of σ-silane hydride species TpRu(PPh 3 )(H a )(η 2 -HbSiR 3 ) ⇆ TpRu(PPh 3 )(H b )(η 2 -H a SiR 3 ). One of the complexes was used for the catalytic hydrolyticoxidation of organosilanes to silanols. A mechanism, which does
X射线晶体学研究表明,将配合物TpRu(PPh 3 )“H 2 SiR 3 ”描述为TpRu(PPh 3 )(η 3 -HSiR 3 H)更合适,一种含有H的静态结构...... Si…H 键而不是高通量的 σ-硅烷氢化物对 TpRu(PPh 3 )(H a )(η 2 -HbSiR 3 ) ⇆ TpRu(PPh 3 )(H b )(η 2 -H a 3)。其中一种配合物用于将有机硅烷催化水解氧化为硅烷醇。提出了一种机制,该机制不涉及通常将硅烷氧化加成到金属中心以形成甲硅烷基氢化物,该机制得到理论计算的支持。
Komarov,N.V.; Igonina,I.I., Journal of general chemistry of the USSR, 1967, vol. 37, p. 1998 - 2001