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二膦 - 酮配体的钴(II)和(I)配合物:硅氢化反应中的催化活性

Cobalt(II) and (I) Complexes of Diphosphine-Ketone Ligands: Catalytic Activity in Hydrosilylation Reactions.

作者信息

Verhoeven Dide G A, Kwakernaak Joost, van Wiggen Maxime A C, Lutz Martin, Moret Marc-Etienne

机构信息

Organic Chemistry & Catalysis Debye Institute for Nanomaterials Science Faculty of Science Utrecht University Universiteitsweg 99 3584 CG Utrecht The Netherlands.

Crystal and Structural Chemistry Bijvoet Center for Biomolecular Research Utrecht University Padualaan 8 3584 CH Utrecht The Netherlands.

出版信息

Eur J Inorg Chem. 2019 Feb 7;2019(5):660-667. doi: 10.1002/ejic.201801221. Epub 2019 Jan 28.

Abstract

The hydrosilylation of unsaturated compounds homogeneously catalyzed by cobalt complexes has gained considerable attention in the last years, aiming at substituting precious metal-based catalysts. In this study, the catalytic activity of well-characterized Co and Co complexes of the dpbp ligand is demonstrated in the hydrosilylation of 1-octene with phenylsilane. The Co complex is the better precatalyst for the mentioned reaction under mild conditions, at 1 mol-% catalyst, 1 h, room temperature, and without solvent, yielding 84 % of octylphenylsilane. Investigation of the substrate scope shows lower performance of the catalyst in styrene hydrosilylation, but excellent results with allylbenzene (84 %) and acetophenone (> 99 %). This catalytic study contributes to the field of cobalt-catalyzed hydrosilylation reactions and shows the first example of catalysis employing the dpbp ligand in combination with a base metal.

摘要

近年来,钴配合物均相催化的不饱和化合物硅氢化反应受到了广泛关注,旨在替代贵金属基催化剂。在本研究中,表征明确的钴和dpbp配体的钴配合物在1-辛烯与苯基硅烷的硅氢化反应中展现出催化活性。在温和条件下,即1 mol-%催化剂、1小时、室温且无溶剂的情况下,钴配合物是上述反应更好的预催化剂,可生成84%的辛基苯基硅烷。底物范围研究表明,该催化剂在苯乙烯硅氢化反应中的性能较低,但在烯丙基苯(84%)和苯乙酮(>99%)的反应中效果优异。这项催化研究为钴催化的硅氢化反应领域做出了贡献,并展示了使用dpbp配体与贱金属结合进行催化的首个实例。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7765/6472597/c36467145158/EJIC-2019-660-g005.jpg

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