Exploring the influence of halogen-substituted Cp*RuX catalysts on RuAAC [3 + 2] cycloaddition: A quantum mechanical investigation”

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-04-03 DOI:10.1016/j.comptc.2025.115223

Ali A. Khairbek , Maha I. Al-Zaben , Ralph Puchta , Renjith Thomas

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Abstract

This study investigated the mechanism of azide-alkyne cycloaddition reactions catalyzed by complexes of ruthenium, specifically Cp*RuX complexes, with various halides (F, Cl, Br, and I). Using the MN12-L/Def2-SVP basis set for all the elements and the Def2-TZVP for Ru (including a pseudopotential for Ru and I) calculations, this research employs an advanced basis set and pseudopotential methods tailored for the elements involved, with a particular focus on the formation of a specific regioisomer. A comparison of the catalytic pathways revealed that the efficiency of the 1,5 pathway surpasses that of the 1,4 pathway in all the examined complexes, particularly when assessed in a common organic solvent. This study highlights the significant role of halogen identity in these complexes, establishing a catalytic activity trend influenced by the halogen used. Detailed analyses using several computational techniques were performed to examine the molecular structures, electron densities, and interactions, demonstrating the potential to enhance catalytic performance by carefully selecting substituted complexes. This research provides valuable insights for designing effective catalysts for click chemistry applications, emphasizing the impact of halogen substitution on catalytic efficiency.

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卤素取代Cp*RuX催化剂对RuAAC[3 + 2]环加成反应影响的量子力学研究

本研究探讨了钌配合物（特别是Cp*RuX配合物）与各种卤化物（F、Cl、Br和I）催化叠氮化物-炔环加成反应的机理。本研究采用了所有元素的MN12-L/Def2-SVP基集和Ru的Def2-TZVP（包括Ru和I的伪势）计算，采用了为所涉及元素定制的先进基集和伪势方法。特别关注特定区域异构体的形成。催化途径的比较表明，1,5途径的效率超过1,4途径在所有检查的配合物，特别是当评估在一个共同的有机溶剂。本研究强调了卤素同一性在这些配合物中的重要作用，建立了受卤素使用影响的催化活性趋势。使用几种计算技术进行了详细的分析，以检查分子结构，电子密度和相互作用，证明了通过仔细选择取代配合物来提高催化性能的潜力。该研究为设计有效的化学催化剂提供了有价值的见解，强调了卤素取代对催化效率的影响。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.