REACTION OF COBALT HYDROTETRACARBONYL WITH OLEFINS
REACTION OF COBALT HYDROTETRACARBONYL WITH OLEFINS
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DOI：
10.1021/ja01480a017
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发表时间：
1961-01-01
影响因子：
15
通讯作者：
BRESLOW, DS
中科院分区：
文献类型：
--
作者：
HECK, RF;BRESLOW, DS
氢化四羰基钴加成到烯烃上形成烷基四羰基钴，作为氢化反应的第一步，已经通过分离所得产物作为它们的单三苯基膦加合物来证明。添加到1-戊烯中，在0时得到的异构体分布与其在高温下的分布大致相同，而添加到异丁烯和丙烯酸甲酯中的方向随温度而变化。加成反应是可逆的。研究CO对加成反应、加合物随后的还原以及烯烃异构化的影响得出的结论是，这些反应涉及配位不饱和物质。提出了加氢反应和烯烃异构化反应的统一机理。
That cobalt hydrotetracarbonyl adds to olefins to form alkylcobalt tetracarbonyls, as the first step in the hydroformylation reaction, has been demonstrated by isolation of the resulting products as their monotriphenylphosphineadducts. Addition to 1-pentene gives approximately the same isomer distribution at 0 that it does at elevated temperatures, whereas the directions of addition to isobutylene and to methyl acrylate change with temperature. Theaddition is reversible. An investigation of the effect of CO on the addition reaction, on the subsequent reduction of the adduct, and on olefin isomerization led to the conclusion that these reactions involve coordinately unsaturated species. A unified mechanismis proposed for the hydroformylation reaction and the concurrent olefinisomerization.