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首页> 外文期刊>Chemistry: A European journal >Computational Approaches to Activity in Rhodium-Catalysed Hydroformylation
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Computational Approaches to Activity in Rhodium-Catalysed Hydroformylation

机译：铑催化加氢甲酰化反应活性的计算方法

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摘要

In this theoretical study on rhodium-catalysed hydroformylation we examine an unmodified hydrido-rhodium(i)carbonyl system a together with three variants modified by the model phosphane ligands PF_3 (system b),PH_3 (system c)and PMe_3 (system d),which show increasing basicity on the Tolman x parameter scale.The ole-finic substrate for all systems is ethene.Based on the dissociative hydroformylation mechanism,static and dynamic quantum-mechanical approaches are made for preequilibria and the whole catalytic cycle.Agreement with experimental results was achieved with regard to the predominance of phosphane monocoordination in systems b-d,different sensitivity of unmodified and modified systems towards hydrogen pressure and the early location of the rate-determining step.Neither the catalytic cycle as a whole nor olefin insertion as an important selectivity-determining step gives a clear picture of activity differences among a-d.However,the crucial first catalytic step,association of ethene to the active species [HRhL_3] (L=CO,PR_3),may play the key role in the experimentally observed higher activity of a and systems with less basic phosphane ligands modelled by b.
机译：在有关铑催化的加氢甲酰化的理论研究中，我们研究了未经修饰的氢化铑（i）羰基系统a以及由模型膦配体PF_3（系统b），PH_3（系统c）和PMe_3（系统d）修饰的三个变体，在Tolman x参数规模上显示出越来越高的基础性。所有系统的烯烃基都是乙烯。基于解离的加氢甲酰基化机理，针对静态和整个催化循环采用了静态和动态的量子力学方法。与实验结果相符关于膦在系统bd中的单配位优势，未改性和改性系统对氢气压力的不同敏感性以及速率确定步骤的早期位置，均实现了这一目标。无论是整个催化循环还是烯烃插入都不是重要的选择性-确定步骤可以清楚地了解广告之间的活性差异。对于活性物质[HRhL_3]（L = CO，PR_3），ne在实验观察到的a和具有b建模的碱性膦配体较少的系统的较高活性中可能起关键作用。

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