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钌在有机-无机杂化共聚物中的固定化:一种用于分子氧氧化醇类的可重复使用的多相催化剂。

Immobilization of ruthenium in organic-inorganic hybrid copolymers: a reusable heterogeneous catalyst for oxidation of alcohols with molecular oxygen.

作者信息

Matsumoto Tsutomu, Ueno Masaharu, Wang Naiwei, Kobayashi Shū

机构信息

Department of Chemistry, School of Science, The University of Tokyo, The HFRE Division, ERATO, Japan and Science Technology Agency, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

出版信息

Chem Asian J. 2008 Feb 1;3(2):239-43. doi: 10.1002/asia.200700336.

Abstract

A novel organic-inorganic hybrid ruthenium (HB Ru) catalyst for the oxidation of alcohols with molecular oxygen has been developed. The catalyst was prepared from a polystyrene-based copolymer, which includes a trimethoxysilyl functionality, and dichlorotris(triphenylphosphine)ruthenium, [RuCl2(PPh3)3], as the metal source. A sol-gel process was employed for heterogenization of the catalyst. The choice of both ruthenium species and trialkoxysilyl-bearing monomers was found to be important for high catalytic activity. In the presence of HB Ru corresponding to 5 mol % loading of ruthenium, the alcohols were oxidized with molecular oxygen or air at atmospheric pressure without any additives to afford the corresponding aldehydes or ketones in good to excellent yields. The catalyst could be recovered and reused at least five times without loss of activity.

摘要

一种用于分子氧氧化醇类的新型有机-无机杂化钌(HB Ru)催化剂已被开发出来。该催化剂由一种基于聚苯乙烯的共聚物制备而成,该共聚物含有三甲氧基硅烷基官能团,以及二氯三(三苯基膦)钌[RuCl₂(PPh₃)₃]作为金属源。采用溶胶-凝胶法对催化剂进行非均相化处理。发现钌物种和含三烷氧基硅烷基的单体的选择对于高催化活性都很重要。在相当于钌负载量5 mol%的HB Ru存在下,醇类在常压下用分子氧或空气氧化,无需任何添加剂,即可得到相应的醛或酮,产率良好至优异。该催化剂可以回收并重复使用至少五次而不失活。

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