Formal Metal-Dependent (M = Pt, Pd) Switching between Arene π-Hole and σ-(Te)-Hole in the Arenetellurium(II) Noncovalent Binding

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2024-11-07 DOI:10.1021/acs.cgd.4c0110410.1021/acs.cgd.4c01104

Anton V. Rozhkov*, Sergi Burguera, Antonio Frontera and Vadim Yu. Kukushkin*,

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Abstract

The diketonate complexes M(acac)₂ (M = Pd (1), Pt (2)) were cocrystallized with bis(perfluoropyridin-4-yl)tellane (Py^F₂Te). Single-crystal X-ray studies of the resulting adducts revealed that the binding mode and stoichiometry between the coformers dramatically depend on the identity of metal sites. Pd(acac)₂ formed adduct 1₃·(Py^F₂Te)₂ where Te···C_acac and π_hole···Pd noncovalent interactions were detected. In contrast to 1, Pt(acac)₂ formed adduct 2·Py^F₂Te where the Te···Pt metal-involving chalcogen bond was observed. Various DFT methods, including the calculation of fully optimized dimeric assemblies and their mutated dimers, allowed for a detailed examination of the corresponding metal-involving noncovalent interactions. Our findings support the notion that metal-involving interactions are the primary structure-determining factors, and the formal transition to the Te···Pt chalcogen bond can be attributed to the increased d_z²-nucleophilicity of the platinum atom compared to the palladium site.

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阿伦碲(II)非共价结合中烯丙基π-孔和σ-(Te)-孔之间的形式金属依赖性（M = Pt、Pd）转换

二酮配合物 M(acac)2（M = Pd (1)、Pt (2)）与双(全氟吡啶-4-基)碲（PyF2Te）共晶体化。对生成的加合物进行的单晶 X 射线研究表明，共形物之间的结合模式和化学计量显著取决于金属位点的特性。Pd(acac)2形成的加合物13-(PyF2Te)2中检测到了Te--Cacac和π孔--Pd的非共价相互作用。与 1 相反，Pt(acac)2 形成了加合物 2-PyF2Te，在该加合物中观察到了 Te--Pt 金属参与的缩醛键。通过各种 DFT 方法，包括计算完全优化的二聚体集合体及其突变的二聚体，可以详细研究相应的金属参与的非共价相互作用。我们的研究结果支持这样一种观点，即涉及金属的相互作用是决定结构的主要因素，而铂原子与钯位点相比，dz2-亲核性更强，因此可以将形式转变归因于Te--Pt链键。

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

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

期刊介绍： The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.