Highly Selective Cobalt-Catalyzed Hydrovinylation of Styrene
Highly Selective Cobalt-Catalyzed Hydrovinylation of Styrene
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DOI：
10.1002/adsc.200900261
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发表时间：
2009-09-01
影响因子：
5.4
通讯作者：
Vogt, Dieter
中科院分区：
文献类型：
--
作者：
Grutters, Michiel M. P.;van der Vlugt, Jarl Ivar;Vogt, Dieter
在苯乙烯加氢乙烯化反应中，由二乙基氯化铝活化的卤化钴盐的磷化配合物显示出高活性的催化剂，对期望产物3-苯基-1-丁烯（3P1B）具有前所未有的高选择性。双键异构化是共聚反应中的一个常见问题，只有在这些催化剂体系完全转化后才会发生，即使在高温下也是如此。最活跃的催化剂是基于卤化钴与C-1或c -2桥接的二膦、异给体P，N或P，O配体、柔性双齿膦配体或单齿膦配体结合的催化剂。动力学研究表明催化剂的> - 1阶，这表明双核物质参与了催化循环或部分催化剂通过双分子途径分解。
Phosphine complexes of cobalt halide salts activated by diethylaluminum chloride are shown to yield highly active catalysts in the hydrovinylation of styrene, with unprecedented high selectivity to the desired product 3-phenyl-1-butene (3P1B). Double-bond isomerization, a common problem in codimerization reactions, only occurs after full conversion with these catalyst systems, even at elevated temperature. The most active catalysts are based on cobalt halide species combined with either C-1- or C-2-bridged diphosphines, heterodonor P,N or P,O ligands, flexible bidentate phosphine ligands or monodentate phosphine ligands. Kinetic investigations show an order > 1 in catalyst, which indicates either the involvement of dinuclear species in the catalytic cycle or partial catalyst decomposition via a bimolecular pathway.