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E-Selective dimerization of phenylacetylene catalyzed by cationic tris(μ-hydroxo)diruthenium(II) complex and the mechanistic insight: The role of two ruthenium centers in catalysis
Journal of Molecular Catalysis A: Chemical Pub Date : 2016-09-02 , DOI: 10.1016/j.molcata.2016.08.027
Sayori Kiyota , Hirofumi Soeta , Nobuyuki Komine , Sanshiro Komiya , Masafumi Hirano

A dinuclear complex [(Me3P)3Ru(μ-OH)3Ru(PMe3)3]+[OPh] (1) (0.5 mol%) catalyzes E-selective dimerization of phenylacetylene, which involves the C–H bond cleavage of phenylacetylene and resulting stereospecific C–C bond forming reaction, at 100 °C for 2 h to give (E)-1,4-diphenylbut-3-en-1-yne in quantitative yield (E/Z = 91/9). Similar reactions using 4-nitro-, 4-cyano-, 4-trifluoromethyl-, 4-acetyl-, and 4-methylphenylacetylene give the corresponding enynes. The kinetic study for dimerization of phenylacetylene shows the second-order and first-order reactions with regard to the phenylacetylene and 1 concentrations, respectively, suggesting this reaction to be catalyzed by a dinuclear ruthenium complex. Addition of PMe3 to the catalytic system strongly discourages the dimerization. These features are consistent with the scenario, where dissociation of a PMe3 ligand from 1 gives a coordinatively unsaturated diruthenium species and one of the ruthenium centers performs as a reaction site for the enyne formation and the other ruthenium center behaves as a spectator in the catalysis.



中文翻译:

阳离子三(μ-羟基)二钌(II)配合物催化的苯乙炔的E选择性二聚和机理研究:两个钌中心在催化中的作用

双核络合物[(Me 3 P)3 Ru(μ-OH)3 Ru(PMe 33 ] + [OPh] -1)(0.5 mol%)催化苯乙炔的E选择性二聚,包括C–苯乙炔的H键裂解及形成的立体定向C–C键形成反应,在100°C下反应2 h,以定量产率得到(E)-1,4-二苯基丁-3-en-1-yne(E / Z = 91/9)。使用4-硝基-,4-氰基-,4-三氟甲基-,4-乙酰基和4-甲基苯基乙炔的类似反应得到相应的烯炔。苯乙炔二聚反应的动力学研究分别显示了有关苯乙炔和1浓度的二级反应和一级反应,表明该反应是由双核钌络合物催化的。将PMe 3加到催化体系中强烈阻碍了二聚作用。这些特征与PMe 3配体从1上解离的情况是一致的。 得到一个配位不饱和的二钌物种,其中一个钌中心充当烯炔形成的反应位点,另一个钌中心充当催化作用的旁观者。

更新日期:2016-09-02
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