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IF 2.3 3区化学 Q3 CHEMISTRY, PHYSICAL

International Journal of Quantum Chemistry Pub Date : 2024-12-11 DOI:10.1002/qua.27522

Gaël Mouzong D'Ambassa, Jean Moto Ongagna, Abel Idrice Adjieufack, Djendo Mazia Suzane Leonie, Désiré Bikele Mama

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引用次数: 0

摘要

本文利用计算工具（B3PW91/LANL2DZ//6-31G(d) 水平），在气相和二甲基亚砜中探讨了亚烷基桥长度和配位模式对一系列 24 个亚烷基桥钯配合物反应活性的影响。这些钯配合物的亚甲基和亚乙基桥长度分别偏好舟型和椅型构型。此外，苯基和硝基络合物的 Pd-C 键活化程度较高，而在亚甲基桥的异常模式下观察到最稳定的 Pd⋯C 相互作用。根据能量分解分析（EDA），两种螯合模式下的氢和苯基络合物都具有更好的静电特性。此外，对于乙烯桥异常配合物（气相），Pd⋯C 的相互作用比 Pd⋯X 的相互作用更强。最后，捐赠/反捐赠比（d/b）值揭示了这些[双（NHC）]⋯[PdX2]相互作用的费歇尔碳烯特性。关于 Pd-C 键金属阳离子周围的杂化，亚甲基桥钯络合物观察到的是 sp2d 类型，而乙烯桥络合物观察到的是 sp3 类型。

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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Deciphering the Influence of Alkylene Bridged and Chelating Mode on Pd—C and Pd—X (X = Cl, Br, and I) Bonding Interaction Within Bis-(NHC)-Palladium Complexes Using Quantum Chemistry Tools

In this paper, we have explored the influence of alkylene-bridged length and coordination mode on the reactivity of a series of 24 alkylene-bridged palladium complexes using computational tools (B3PW91/LANL2DZ//6-31G(d) level) in gas phase and DMSO. These palladium complexes prefer a boat and chair configuration for methylene and ethylene bridge length, respectively. In addition, phenyl and nitro complexes present a higher activation for Pd—C bonds while the most stable Pd⋯C interactions are observed for abnormal mode with methylene bridge. According to the energy decomposition analysis (EDA), hydrogen and phenyl complexes in both chelation modes present a better electrostatic character. Moreover, Pd⋯C interactions are stronger compared to the Pd⋯X ones for ethylene-bridged abnormal complexes (in gas phase). Finally, the donation/back-donation ratio (d/b) values reveal the Fischer carbene character of these [bis(NHC)]⋯[PdX₂] interactions. Concerning the hybridization around the metal cation for the Pd—C bond, the sp²d type is observed for methylene-bridged palladium complexes while the sp³ one is observed for ethylene bridge complexes.

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来源期刊

International Journal of Quantum Chemistry 化学-数学跨学科应用

CiteScore

4.70

自引率

4.50%

发文量

185

审稿时长

2 months

期刊介绍： Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.