Stabilizing Halogen-Bonded Complex between Metallic Anion and Iodide
Halogen bonds (XBs) between metal anions and halides have seldom been reported because metal anions are reactive for XB donors. The pyramidal-shaped Mn(CO)<sub>5</sub><sup>−</sup> anion is a candidate metallic XB acceptor with a ligand-protected metal core that maintains the...
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MDPI AG
2022-11-01
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| author | Fei Ying Xu Yuan Xinxing Zhang Jing Xie |
| author_facet | Fei Ying Xu Yuan Xinxing Zhang Jing Xie |
| author_sort | Fei Ying |
| collection | DOAJ |
| description | Halogen bonds (XBs) between metal anions and halides have seldom been reported because metal anions are reactive for XB donors. The pyramidal-shaped Mn(CO)<sub>5</sub><sup>−</sup> anion is a candidate metallic XB acceptor with a ligand-protected metal core that maintains the negative charge and an open site to accept XB donors. Herein, Mn(CO)<sub>5</sub><sup>−</sup> is prepared by electrospray ionization, and its reaction with CH<sub>3</sub>I in gas phase is studied using mass spectrometry and density functional theory (DFT) calculation. The product observed experimentally at m/z = 337 is assigned as [IMn(CO)<sub>4</sub>(OCCH<sub>3</sub>)]<sup>−</sup>, which is formed by successive nucleophilic substitution and reductive elimination, instead of the halogen-bonded complex (XC) CH<sub>3</sub>−I···Mn(CO)<sub>5</sub><sup>−</sup>, because the I···Mn interaction is weak within XC and it could be a transient species. Inspiringly, DFT calculations predict that replacing CH<sub>3</sub>I with CF<sub>3</sub>I can strengthen the halogen bonding within the XC due to the electro-withdrawing ability of F. More importantly, in so doing, the nucleophilic substitution barrier can be raised significantly, ~30 kcal/mol, thus leaving the system trapping within the XC region. In brief, the combination of a passivating metal core and the introduction of an electro-withdrawing group to the halide can enable strong halogen bonding between metallic anion and iodide. |
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| language | English |
| last_indexed | 2024-03-09T18:07:29Z |
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| series | Molecules |
| spelling | doaj.art-eeea43808c004149b985fa1603f1c7d52023-11-24T09:25:58ZengMDPI AGMolecules1420-30492022-11-012722806910.3390/molecules27228069Stabilizing Halogen-Bonded Complex between Metallic Anion and IodideFei Ying0Xu Yuan1Xinxing Zhang2Jing Xie3Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, ChinaCollege of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center (ReCAST), Tianjin Key Laboratory of Biosensing and Molecular Recognition, Shenzhen Research Institute, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, ChinaCollege of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center (ReCAST), Tianjin Key Laboratory of Biosensing and Molecular Recognition, Shenzhen Research Institute, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, ChinaKey Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, ChinaHalogen bonds (XBs) between metal anions and halides have seldom been reported because metal anions are reactive for XB donors. The pyramidal-shaped Mn(CO)<sub>5</sub><sup>−</sup> anion is a candidate metallic XB acceptor with a ligand-protected metal core that maintains the negative charge and an open site to accept XB donors. Herein, Mn(CO)<sub>5</sub><sup>−</sup> is prepared by electrospray ionization, and its reaction with CH<sub>3</sub>I in gas phase is studied using mass spectrometry and density functional theory (DFT) calculation. The product observed experimentally at m/z = 337 is assigned as [IMn(CO)<sub>4</sub>(OCCH<sub>3</sub>)]<sup>−</sup>, which is formed by successive nucleophilic substitution and reductive elimination, instead of the halogen-bonded complex (XC) CH<sub>3</sub>−I···Mn(CO)<sub>5</sub><sup>−</sup>, because the I···Mn interaction is weak within XC and it could be a transient species. Inspiringly, DFT calculations predict that replacing CH<sub>3</sub>I with CF<sub>3</sub>I can strengthen the halogen bonding within the XC due to the electro-withdrawing ability of F. More importantly, in so doing, the nucleophilic substitution barrier can be raised significantly, ~30 kcal/mol, thus leaving the system trapping within the XC region. In brief, the combination of a passivating metal core and the introduction of an electro-withdrawing group to the halide can enable strong halogen bonding between metallic anion and iodide.https://www.mdpi.com/1420-3049/27/22/8069halogen bondmetallic anionnucleophilic substitution reactionquantum chemistry calculationreductive elimination |
| spellingShingle | Fei Ying Xu Yuan Xinxing Zhang Jing Xie Stabilizing Halogen-Bonded Complex between Metallic Anion and Iodide Molecules halogen bond metallic anion nucleophilic substitution reaction quantum chemistry calculation reductive elimination |
| title | Stabilizing Halogen-Bonded Complex between Metallic Anion and Iodide |
| title_full | Stabilizing Halogen-Bonded Complex between Metallic Anion and Iodide |
| title_fullStr | Stabilizing Halogen-Bonded Complex between Metallic Anion and Iodide |
| title_full_unstemmed | Stabilizing Halogen-Bonded Complex between Metallic Anion and Iodide |
| title_short | Stabilizing Halogen-Bonded Complex between Metallic Anion and Iodide |
| title_sort | stabilizing halogen bonded complex between metallic anion and iodide |
| topic | halogen bond metallic anion nucleophilic substitution reaction quantum chemistry calculation reductive elimination |
| url | https://www.mdpi.com/1420-3049/27/22/8069 |
| work_keys_str_mv | AT feiying stabilizinghalogenbondedcomplexbetweenmetallicanionandiodide AT xuyuan stabilizinghalogenbondedcomplexbetweenmetallicanionandiodide AT xinxingzhang stabilizinghalogenbondedcomplexbetweenmetallicanionandiodide AT jingxie stabilizinghalogenbondedcomplexbetweenmetallicanionandiodide |