A comprehensive study on the synthesis, X-ray characterization, and theoretical investigation of new dimeric palladium(II) complexes of phosphonium ylides

IF 2.2 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Structural Chemistry Pub Date : 2025-02-22 DOI:10.1007/s11224-025-02469-8

Faezeh Moniriyan, Seyyed Javad Sabounchei, Asieh Sedghi, Robert W. Gable

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引用次数: 0

Abstract

A new series of palladium(II) complexes with α-keto-stabilized phosphonium ylide ligands having a general formula [Pd(μ-X)(PPh₃CHC(O)C₆H₄R)]₂ [X = Br, R = m-OCH₃ (C1), p-NO₂ (C2), p-F (C3), X = Cl, R = m-OCH₃ (C4)] was prepared. Also, a single-crystal X-ray diffraction study was performed for the compounds C1 and C4, which revealed a dimeric square-planar geometry around Pd(II) ions for these complexes. The spectroscopic and crystallographic results indicate that the phosphonium ylides coordinate to palladium(II) centers through the coordinatively active ylidic carbon atom and ortho-carbon atom of PPh₃ phenyl ring (ortho-palladation). Using theoretical methods, density function theory (DFT) calculations at the BP86/def2-SVP level of theory, the structures of dimeric palladium(II) [Pd(μ-Br)(PPh₃CHC(O)C₆H₄R)]₂ [R = p-OCH₃ (a), R = p-NO₂ (b), p-F (c)] complexes were investigated. The strength and nature of donor − acceptor bonds between the phosphonium ylide (L) and Pd fragments were analyzed using natural bond orbital analysis (NBO).

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新型二聚钯（II）配合物的合成、x射线表征及理论研究

制备了一系列新的α-酮稳定的磷酰化配体钯配合物，其通式为[Pd(μ-X)(PPh3CHC(O)C6H4R)]2 [X = Br, R = m-OCH3 (C1), p-NO2 (C2), p-F (C3), X = Cl, R = m-OCH3 (C4)]。此外，对化合物C1和C4进行了单晶x射线衍射研究，揭示了这些配合物在Pd（II）离子周围的二聚体方形平面几何结构。光谱学和晶体学结果表明，磷基化合物是通过PPh3苯基环的配位活性基碳原子和邻位碳原子与钯（II）中心配位的。采用理论方法，在BP86/def2-SVP水平上进行密度泛函理论（DFT）计算，研究了二聚体钯（II） [Pd(μ-Br)(PPh3CHC(O)C6H4R)]2 [R = p-OCH3 (a), R = p-NO2 (b), p-F (c)]配合物的结构。利用自然键轨道分析（NBO）分析了磷酰化(L)和钯片段之间供体-受体键的强度和性质。

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来源期刊

Structural Chemistry 化学-化学综合

CiteScore

3.80

自引率

11.80%

发文量

227

审稿时长

3.7 months

期刊介绍： Structural Chemistry is an international forum for the publication of peer-reviewed original research papers that cover the condensed and gaseous states of matter and involve numerous techniques for the determination of structure and energetics, their results, and the conclusions derived from these studies. The journal overcomes the unnatural separation in the current literature among the areas of structure determination, energetics, and applications, as well as builds a bridge to other chemical disciplines. Ist comprehensive coverage encompasses broad discussion of results, observation of relationships among various properties, and the description and application of structure and energy information in all domains of chemistry. We welcome the broadest range of accounts of research in structural chemistry involving the discussion of methodologies and structures,experimental, theoretical, and computational, and their combinations. We encourage discussions of structural information collected for their chemicaland biological significance.