Hydrovinylation of styrene derivatives to 3-aryl-1-butenes catalysed by nickel complexes

Q4 Chemical Engineering

分子催化 Pub Date : 1994-08-30 DOI:10.1016/0304-5102(94)00066-2

R. Ceder, G. Muller, J.I. Ordinas

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引用次数: 20

Abstract

The hydrovinylation of styrene and ring-substituted styrene molecules by the ionic nickel precursor trans-[Ni(2,4,6-Me₃C₆H₂) (CH₃CN) (P(CH₂Ph)₃)₂]BF₄ in THF solution has been investigated. The chemoselectivity towards hydrovinylation products is about 99%. For styrene the conversion is nearly complete and the regioselectivity towards the vinylation in the α-position in the conjugated aryl olefin derivatives is 100%. The yield of 3-phenyl-1-butene reaches 97% with minor amounts of the isomerization products cis- and trans-2-phenyl-2-butene. The turnover rate of the reaction at 25°C, 15 bar (initial pressure) of ethylene with a styrene/[Ni] ratio 1000/1 is 1915 h⁻¹. With styrene derivatives substituted in the vinyl fragment, the hydrovinylation reaction was very limited; however those substituted in the phenyl fragment (ArCH=CH₂; Ar:p- and m-Me(C₆H₄), p- and m-Et(C₆H₄), p-and m-vinyl(C₆H₄), p- and m-Cl(C₆H₄), p-MeO(C₆H₄) and m-NO₂(C₆H₄)) showed similar selectivity to styrene but different turnover rates. Activity decreases with the substituent in the sequence Cl∼OMe∼CH=CH₂∼H∼CH₂CH₃&>;Me&>;NO₂ related with the coordination ability of the olefin. Activity of the para derivatives is slightly higher than that of the meta analogues. The ionic compound [Ni(2,4,6-Me₃C₆H₂) (CH₃CN) ((PhCH₂)₂PCH₂CH₂P(CH₂Ph)₂)]BF₄ and the neutral trans-[NiBr(2,4,6-Me₃C₆H₂) (P(CH₂Ph)₃)₂] do not show any activity in the codimerization reaction of styrene and ethylene in the same conditions.

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镍配合物催化苯乙烯衍生物加氢乙烯化制3-芳基-1-丁烯

研究了离子镍前驱体反式[Ni(2,4,6- me3c6h2) (CH3CN) (P(CH2Ph)3)2]BF4在THF溶液中对苯乙烯和环取代苯乙烯分子的加氢乙烯化反应。对加氢乙烯化产物的化学选择性约为99%。对于苯乙烯，转化基本完成，共轭芳基烯烃衍生物中α-位乙烯化的区域选择性为100%。3-苯基-1-丁烯的收率达97%，异构化产物中有少量顺式和反式-2-苯基-2-丁烯。在25℃，15 bar(初始压力)条件下，苯乙烯/[Ni]比为1000/1的乙烯的反应周转率为1915 h−1。在乙烯基片段中取代苯乙烯衍生物后，加氢乙烯化反应非常有限;而取代在苯基片段(ArCH=CH2;Ar:p-和m-Me(C6H4)、p-和m-Et(C6H4)、p-和m-乙烯基(C6H4)、p-和m-Cl(C6H4)、p- meo (C6H4)和m-NO2(C6H4))对苯乙烯的选择性相似，但转化率不同。活性随着取代基Cl ~ OMe ~ CH=CH2 ~ H ~ CH2CH3&>;Me&>;NO2的顺序而降低，NO2与烯烃的配位能力有关。para衍生物的活性略高于meta类似物。离子化合物[Ni(2,4,6- me3c6h2) (CH3CN) ((PhCH2)2PCH2CH2P(CH2Ph)2)]BF4和中性反式-[NiBr(2,4,6- me3c6h2) (P(CH2Ph)3)2]在相同条件下对苯乙烯和乙烯的共聚反应没有表现出任何活性。

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来源期刊

分子催化 Chemical Engineering-Catalysis

CiteScore

1.50

自引率

0.00%

发文量

2959

期刊介绍： Journal of Molecular Catalysis (China) is a bimonthly journal, founded in 1987. It is a bimonthly journal, founded in 1987, sponsored by Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, under the supervision of Chinese Academy of Sciences, and published by Science Publishing House, which is a scholarly journal openly circulated both at home and abroad. The journal mainly reports the latest progress and research results on molecular catalysis. It contains academic papers, research briefs, research reports and progress reviews. The content focuses on coordination catalysis, enzyme catalysis, light-ribbed catalysis, stereochemistry in catalysis, catalytic reaction mechanism and kinetics, the study of catalyst surface states and the application of quantum chemistry in catalysis. We also provide contributions on the activation, deactivation and regeneration of homogeneous catalysts, solidified homogeneous catalysts and solidified enzyme catalysts in industrial catalytic processes, as well as on the optimisation and characterisation of catalysts for new catalytic processes. The main target readers are scientists and postgraduates working in catalysis in research institutes, industrial and mining enterprises, as well as teachers and students of chemistry and chemical engineering departments in colleges and universities. Contributions from related professionals are welcome.