Synthesis and investigation of the thermal stability of siliconcontaining esters of phosphorus acids. 2. Thermal rearrangement of trimethylsilylmethyl (?siliconeopentyl?) esters of phosphorus acids
NaY Zeolite as Host for the Selective Heterogeneous Oxidation of Silanes and Olefins with Hydrogen Peroxide Catalyzed by Methyltrioxorhenium
作者:Waldemar Adam、Chantu R. Saha-Möller、Oliver Weichold
DOI:10.1021/jo991908e
日期:2000.5.1
The methyltrioxorhenium(MTO)-catalyzed oxidation of silanes to silanols and the epoxidation of various olefins by aqueous 85% H(2)O(2) proceed in high yields and excellent product selectivities (no disiloxanes, diols) in the presence of the zeolite NaY. The oxidative species is located inside the 12-A supercages. This prevents the bimolecular condensation of the silanol to disiloxane by steric means
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 (
Size does matter: The nonporous tetra‐n‐butylammonium salt of silicodecatungstate, synthesized through a bottom‐up approach, heterogeneously catalyzes the size‐selective oxidation of various organic compounds, including olefins, sulfides, and organosilanes, with aqueous H2O2 in ethyl acetate. The catalyst can be easily separated by filtration and reused several times with retention of high catalytic
大小确实很重要:通过自下而上的方法合成的无孔硅酸四硅烷基四正丁铵盐,可在H 2 O 2水溶液中以非均相催化催化各种有机化合物的尺寸选择氧化,包括烯烃,硫化物和有机硅烷。乙酸乙酯。可以通过过滤容易地分离催化剂,并在保持高催化活性的情况下重复使用数次。
Organocatalytic Oxidation of Organosilanes to Silanols
作者:Dimitris Limnios、Christoforos G. Kokotos
DOI:10.1021/cs400515w
日期:2013.10.4
The oxidation of organosilanes to silanols constitutes an attractive transformation for both industry and academia. Bypassing the need for stoichiometric oxidants or precious metal catalytic complexes, the first organocatalytic oxidation of silanes has been accomplished. Catalytic amounts of 2,2,2-trifluoroacetophenone, in combination with the green oxidant H2O2, lead to excellent to quantitative yields
有机硅烷氧化为硅烷醇构成了工业界和学术界的诱人转变。绕过对化学计量的氧化剂或贵金属催化络合物的需求,已经完成了硅烷的第一有机催化氧化。催化量的2,2,2-三氟苯乙酮与绿色氧化剂H 2 O 2结合,可在较短的反应时间内达到极佳的定量收率。可以容许各种烷基,芳基,烯基和炔基取代基,从而为高度希望的转化提供了一种简单,廉价,有效和实用的解决方案。
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。