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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Computational insights into carbon–carbon homocoupling reactions mediated by organolanthanide(III) complexes?
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Computational insights into carbon–carbon homocoupling reactions mediated by organolanthanide(III) complexes?

机译：关于有机镧系元素（III）配合物介导的碳-碳均偶联反应的计算见解？

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摘要

Homocoupling of terminal alkynes into trienediyl complexes by alkyl samarocenes is known experimentally. By means of computational techniques, we investigated the mechanism of this reaction in detail. The overall reaction sequence is: σ-bond metathesis, dimerisation of metallocenes, and homocoupling of two acetylides into trienediyl. We show that the rate-determining step corresponds to the homocoupling of two anionic acetylides. This coupling takes place at a bis-samarocene dimer complex in which the bridging mode of the two acetylide moieties is critical for the reaction to proceed. The limited energy barrier for the homocoupling of the carbanions originates from a synergistic effect of the two samarium centres within the dimer. Variation of the steric demand of both substrates and lanthanocenes allowed rationalising all the experimental data available for these systems.
机译：在实验上已知末端炔烃通过烷基三茂烯的均偶联为三烯二基络合物。通过计算技术，我们详细研究了该反应的机理。总体反应顺序为：σ键复分解，茂金属的二聚化以及两个乙炔化物均化为三烯二基。我们表明速率确定步骤对应于两个阴离子乙炔化物的均偶联。这种偶合发生在双-三茂铁二聚体络合物中，其中两个乙炔基部分的桥接方式对于反应的进行至关重要。碳负离子均相耦合的有限能垒来自二聚体中两个sa中心的协同作用。底物和镧系元素的空间需求的变化允许合理化所有可用于这些系统的实验数据。

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