在本报告中,我们介绍了六种新型中性铂配合物的合成,使用容易获得的 P,N-供体配体,通过简单的两步程序合成。随后,我们研究了它们在末端烯烃加氢元素化中的催化活性,强调了它们在材料和天然产物化学中的多功能用途。在低催化剂负载量下,硅、锗和氢化硼仅以反马尔可夫尼科夫方式有效加成到 CC 键上。此外,我们的底物范围涵盖广泛的脂肪族和芳香族烯烃,其取代基具有不同的电子特性。与许多以前的 Pt 配合物相比,我们的催化系统对其他不饱和官能团(例如羰基和内部 CC 键)表现出卓越的化学选择性。值得注意的是,它还表现出对羟基、烷氧基、甲硅烷基和硫醚部分的显着耐受性。此外,我们还强调了催化剂的性能,展示了其在多个催化循环中保持一致的活性和选择性的能力。
dioxide (Co/TiO2) catalyst was synthesized by hydrogen treatment method. The Co/TiO2 catalyst acts as a highly efficient heterogeneous catalyst for the anti-Markovnikov hydrosilylation of alkenes under solvent-free conditions. Various alkenes were selectively converted to the corresponding alkylsilanes. This catalyst showed high stability in air and high reusability with maintained activity. The investigation
烯烃的氢化硅烷化对于有机硅化合物的合成很重要,为此,贵金属络合物已用作工业催化剂。考虑到环境和经济问题,强烈期望开发具有高稳定性,易分离性和高可重复使用性的富含地球的金属催化剂。在本文中,我们报道了通过氢处理方法合成了一种新型的钴离子掺杂的二氧化钛(Co / TiO 2)催化剂。Co / TiO 2催化剂在无溶剂条件下用作烯烃的反马尔可夫尼科夫氢化硅烷化反应的高效多相催化剂。将各种烯烃选择性地转化为相应的烷基硅烷。该催化剂在空气中显示出高稳定性,并在保持活性的情况下具有高可重复使用性。活性位点结构和Co的催化性能之间的关系的调查/的TiO 2公开了Co的高稳定性和耐用性/二氧化钛2都是起源选自Co和TiO之间的强相互作用2通过CoTiO形成3固溶体物种。
Visible-Light-Mediated Metal-Free Hydrosilylation of Alkenes through Selective Hydrogen Atom Transfer for Si−H Activation
Although there has been significant progress in the development of transition‐metal‐catalyzed hydrosilylations of alkenes over the past several decades, metal‐free hydrosilylation is still rare and highly desirable. Herein, we report a convenient visible‐light‐drivenmetal‐free hydrosilylation of both electron‐deficient and electron‐rich alkenes that proceeds through selective hydrogen atom transfer
Hydrosilylation Reaction Catalysts and Curable Compositions and Methods for Their Preparation and Use
申请人:Dow Corning Corporation
公开号:US20140296468A1
公开(公告)日:2014-10-02
A composition contains (A) a hydrosilylation reaction catalyst and (B) an aliphatically unsaturated compound having an average, per molecule, of one or more aliphatically unsaturated organic groups capable of undergoing hydrosilylation reaction. The composition is capable of reacting via hydrosilylation reaction to form a reaction product, such as a silane, a gum, a gel, a rubber, or a resin. Ingredient (A) contains an iron-organosilicon ligand complex that can be prepared by reacting an iron carbonyl compound and an organosilicon ligand.
(Aminomethyl)pyridine Complexes for the Cobalt‐Catalyzed Anti‐Markovnikov Hydrosilylation of Alkoxy‐ or Siloxy(vinyl)silanes with Alkoxy‐ or Siloxyhydrosilanes
作者:Kangsang L. Lee
DOI:10.1002/anie.201612460
日期:2017.3.20
Cobalt‐catalyzed anti‐Markovnikov reactions that involve siloxy‐ or alkoxy(vinyl)silanes and siloxy‐ or alkoxyhydrosilanes are disclosed. More than 25 new cobalt–(aminomethyl)pyridine complexes were developed as catalysts for the hydrosilylation of industry‐relevant and challenging siloxy‐ or alkoxy‐terminated vinylsilanes. These transformations typically proceed in the presence of 0.25 mol % of the
including late-stage functionalization and radical cascade reactions. Furthermore, this technology could be extended to the construction of C–B, C–S and C–Sn bonds, thus offering a versatile platform for bond activation and connection of main group elements. The green aspect of the reaction has also been demonstrated by using Brij-30/water as a reaction solvent or sunlight as an alternative energy source