Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)Pd<sup>II</sup> Complexes
Binuclear diaminocarbene complexes, which form as a regioisomer mixture in the reaction between isocyanide–palladium(II) complex <i>cis</i>-[PdCl<sub>2</sub>(CNXyl)<sub>2</sub>] and 1,3-thiazol-2-amine, are able to exchange an anionic chloride ligand with other ha...
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MDPI AG
2023-06-01
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| Series: | Inorganics |
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| author | Roman A. Popov Alexander S. Novikov Vitalii V. Suslonov Vadim P. Boyarskiy |
| author_facet | Roman A. Popov Alexander S. Novikov Vitalii V. Suslonov Vadim P. Boyarskiy |
| author_sort | Roman A. Popov |
| collection | DOAJ |
| description | Binuclear diaminocarbene complexes, which form as a regioisomer mixture in the reaction between isocyanide–palladium(II) complex <i>cis</i>-[PdCl<sub>2</sub>(CNXyl)<sub>2</sub>] and 1,3-thiazol-2-amine, are able to exchange an anionic chloride ligand with other halides, such as Br or I. This process also affords binuclear complexes as mixtures of kinetically and thermodynamically controlled regioisomers. In CDCl<sub>3</sub> solutions, we observed interconversion of kinetically and thermodynamically controlled regioisomers. The results of the DFT calculations revealed that in CHCl<sub>3</sub> solution, each pair of the isomers exhibited two different types of chalcogen bonding such as S···X or S···N; the presence of CBs for two complexes in the solid state was also proven through X-ray crystallographic study. Based on the combined experimental and theoretical data, it could be concluded that thermodynamic favorability for the formation of thermodynamically controlled regioisomers increases in the Cl < Br ≈ I row and correlate well with the energy difference between S···N and S···X (X = Cl, Br, I) chalcogen bonds in kinetically and thermodynamically controlled products. This means that it is possible to change the structure of metallocycles in binuclear diaminocarbene complexes by simply replacing one halide ligand with another. |
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| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-03-11T02:19:34Z |
| publishDate | 2023-06-01 |
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| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-9acb063672124832a8ebfd6009a149f42023-11-18T10:55:25ZengMDPI AGInorganics2304-67402023-06-0111625510.3390/inorganics11060255Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)Pd<sup>II</sup> ComplexesRoman A. Popov0Alexander S. Novikov1Vitalii V. Suslonov2Vadim P. Boyarskiy3Institute of Chemistry, Saint Petersburg State University, 26 Universitetskii Prospect, Petergof, St. Petersburg 198504, RussiaInstitute of Chemistry, Saint Petersburg State University, 26 Universitetskii Prospect, Petergof, St. Petersburg 198504, RussiaInstitute of Chemistry, Saint Petersburg State University, 26 Universitetskii Prospect, Petergof, St. Petersburg 198504, RussiaInstitute of Chemistry, Saint Petersburg State University, 26 Universitetskii Prospect, Petergof, St. Petersburg 198504, RussiaBinuclear diaminocarbene complexes, which form as a regioisomer mixture in the reaction between isocyanide–palladium(II) complex <i>cis</i>-[PdCl<sub>2</sub>(CNXyl)<sub>2</sub>] and 1,3-thiazol-2-amine, are able to exchange an anionic chloride ligand with other halides, such as Br or I. This process also affords binuclear complexes as mixtures of kinetically and thermodynamically controlled regioisomers. In CDCl<sub>3</sub> solutions, we observed interconversion of kinetically and thermodynamically controlled regioisomers. The results of the DFT calculations revealed that in CHCl<sub>3</sub> solution, each pair of the isomers exhibited two different types of chalcogen bonding such as S···X or S···N; the presence of CBs for two complexes in the solid state was also proven through X-ray crystallographic study. Based on the combined experimental and theoretical data, it could be concluded that thermodynamic favorability for the formation of thermodynamically controlled regioisomers increases in the Cl < Br ≈ I row and correlate well with the energy difference between S···N and S···X (X = Cl, Br, I) chalcogen bonds in kinetically and thermodynamically controlled products. This means that it is possible to change the structure of metallocycles in binuclear diaminocarbene complexes by simply replacing one halide ligand with another.https://www.mdpi.com/2304-6740/11/6/255chalcogen bonding(Diaminocarbene)Pd<sup>II</sup> complexesregioisomerizationhalogen-dependent equilibrium |
| spellingShingle | Roman A. Popov Alexander S. Novikov Vitalii V. Suslonov Vadim P. Boyarskiy Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)Pd<sup>II</sup> Complexes Inorganics chalcogen bonding (Diaminocarbene)Pd<sup>II</sup> complexes regioisomerization halogen-dependent equilibrium |
| title | Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)Pd<sup>II</sup> Complexes |
| title_full | Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)Pd<sup>II</sup> Complexes |
| title_fullStr | Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)Pd<sup>II</sup> Complexes |
| title_full_unstemmed | Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)Pd<sup>II</sup> Complexes |
| title_short | Molecular Switching through Chalcogen-Bond-Induced Isomerization of Binuclear (Diaminocarbene)Pd<sup>II</sup> Complexes |
| title_sort | molecular switching through chalcogen bond induced isomerization of binuclear diaminocarbene pd sup ii sup complexes |
| topic | chalcogen bonding (Diaminocarbene)Pd<sup>II</sup> complexes regioisomerization halogen-dependent equilibrium |
| url | https://www.mdpi.com/2304-6740/11/6/255 |
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