1. The nature of π-hole spodium bonds in the HgLCl2(L = pyrrole, pyrazole, imidazole, pyridine, pyridazine, and pyrimidine) complexes: from noncovalent to covalent interactions.
- Author
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Tian, Rong, Zeng, Yanli, Li, Xiaoyan, and Zhang, Xueying
- Subjects
COORDINATE covalent bond ,PYRROLES ,PYRAZOLES ,PYRIMIDINES ,PYRIDINE ,IMIDAZOLES ,PYRIDAZINES - Abstract
The nature of π-hole spodium bonds in the HgLCl
2 ⋯ZH3 /CH2 Y complexes (L = pyrrole 1, pyrazole 2, imidazole 3, pyridine 4, pyridazine 5, and pyrimidine 6; Z = N, P, As, and Sb; Y = O, S, Se, and Te) has been studied using theoretical calculations. The electrophilicity of the π-hole in the tri-coordinated HgII complexes varies with the type of N-heterocyclic ligand. The strength and nature of the π-hole spodium bond is closely related to the properties of the Lewis bases. In the case of HgLCl2 ⋯ZH3 , the strength of the π-hole spodium bond weakens as the nucleophilicity of the base decreases, following the sequence HgLCl2 ⋯NH3 > HgLCl2 ⋯PH3 > HgLCl2 ⋯AsH3 > HgLCl2 ⋯SbH3 . The Hg⋯Z spodium bonds change from a partially covalent interaction to a close-shelled noncovalent interaction. The nucleophilic ability of CH2 Y decreases in the order CH2 O > CH2 S > CH2 Se > CH2 Te, while the strength of the π-hole spodium bond follows the order HgLCl2 ⋯OCH2 < HgLCl2 ⋯SCH2 < HgLCl2 ⋯SeCH2 < HgLCl2 ⋯TeCH2 . The Hg⋯Y spodium bond undergoes a transition from a close-shelled noncovalent to a partially covalent interaction, resulting in an incremental increase in the degree of covalence. The Hg⋯Te spodium bond exhibits certain characteristics resembling those of a coordinate covalent bond. The inter-orbital interactions observed in the formation of the HgLCl2 ⋯YCH2 complexes appear to be significantly stronger compared to those observed in the HgLCl2 ⋯ZH3 complexation. [ABSTRACT FROM AUTHOR]- Published
- 2024
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