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Kinetics and Mechanistic Insights into the Acetate-Assisted Dimerization of Terminal Alkynes under Ruthenium- and Acid-Promoted (RAP) Catalysis
Organometallics ( IF 2.5 ) Pub Date : 2017-09-21 00:00:00 , DOI: 10.1021/acs.organomet.7b00583 Riccardo Salvio 1 , Francisco Juliá-Hernández 1 , Luca Pisciottani 1 , Rafael Mendoza-Meroño 2 , Santiago García-Granda 2 , Mauro Bassetti 1
Organometallics ( IF 2.5 ) Pub Date : 2017-09-21 00:00:00 , DOI: 10.1021/acs.organomet.7b00583 Riccardo Salvio 1 , Francisco Juliá-Hernández 1 , Luca Pisciottani 1 , Rafael Mendoza-Meroño 2 , Santiago García-Granda 2 , Mauro Bassetti 1
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The mechanism of the dimerization of terminal aryl alkynes promoted by [{RuCl(μ-Cl)(η6-p-cymene)}2](1)/AcOH, under cooperative transition metal/Brønsted acid catalysis, has been investigated with regard to (i) the activation of the dinuclear ruthenium complex and (ii) the catalytic formation of the trans-1,4-diaryl-1,3-enyne products, by a detailed kinetic investigation of both processes. Complex 1 is subject to a slow solvolytic process in neat acetic acid or is transformed rapidly in the presence of sodium acetate to form the monomeric ruthenium(II) acetato complex [RuCl(η6-p-cymene)(OAc)]. The latter is the active catalytic species promoting the alkyne dimerization process, via initial π-alkyne coordination and intramolecular C–H abstraction by the acetate ligand, as key steps of the catalytic cycle. The presence of additive acetate salts allows for the reaction to proceed at room temperature with short reaction times and high trans/cis stereoselectivity, thus rendering this catalytic system among the most active and selective procedures for the dimerization of terminal alkynes in a protic medium. The linear coupling of three molecules of phenylacetylene affords an organometallic ruthenium complex featuring a butenynyl ligand which has been characterized by X-ray crystallography.
中文翻译：
在钌和酸促进（RAP）催化下，乙酸酯辅助末端炔烃的二聚反应的动力学和力学见解
通过推动末端芳炔的二聚化的机制[{的RuCl（μ-Cl）的（η 6 - p -cymene）} 2 ]（1）/ AcOH中，下合作过渡金属/布朗斯台德酸催化，已经研究了关于（i）通过对这两个过程进行详细的动力学研究，来活化双核钌配合物和（ii）催化形成反式-1,4-二芳基-1,3-烯炔产物。复杂1经受在纯乙酸的缓慢溶剂化过程或在乙酸钠存在下快速转化以形成单体钌（II）乙酸根络合物将[RuCl（η 6 - p-cymene）（OAc）]。后者是通过最初的π-炔基配位和通过乙酸酯配体的分子内C-H提取来促进炔烃二聚化过程的活性催化物质，是催化循环的关键步骤。添加剂乙酸盐的存在使反应可以在室温下以较短的反应时间和高的反式/顺式立体选择性进行，从而使该催化体系成为质子介质中末端炔烃二聚化的最活跃和选择性的方法之一。苯乙炔的三个分子的线性偶合提供了具有丁炔基配体的有机金属钌配合物，该配合物已通过X射线晶体学表征。
更新日期：2017-09-21
中文翻译：
在钌和酸促进（RAP）催化下，乙酸酯辅助末端炔烃的二聚反应的动力学和力学见解
通过推动末端芳炔的二聚化的机制[{的RuCl（μ-Cl）的（η 6 - p -cymene）} 2 ]（1）/ AcOH中，下合作过渡金属/布朗斯台德酸催化，已经研究了关于（i）通过对这两个过程进行详细的动力学研究，来活化双核钌配合物和（ii）催化形成反式-1,4-二芳基-1,3-烯炔产物。复杂1经受在纯乙酸的缓慢溶剂化过程或在乙酸钠存在下快速转化以形成单体钌（II）乙酸根络合物将[RuCl（η 6 - p-cymene）（OAc）]。后者是通过最初的π-炔基配位和通过乙酸酯配体的分子内C-H提取来促进炔烃二聚化过程的活性催化物质，是催化循环的关键步骤。添加剂乙酸盐的存在使反应可以在室温下以较短的反应时间和高的反式/顺式立体选择性进行，从而使该催化体系成为质子介质中末端炔烃二聚化的最活跃和选择性的方法之一。苯乙炔的三个分子的线性偶合提供了具有丁炔基配体的有机金属钌配合物，该配合物已通过X射线晶体学表征。
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