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Stabilizing Halogen-Bonded Complex between Metallic Anion and Iodide.
| Content Provider | Europe PMC |
|---|---|
| Author | Ying, Fei Yuan, Xu Zhang, Xinxing Xie, Jing |
| Editor | Li, Qingzhong Scheiner, Steve Yu, Zhiwu |
| Copyright Year | 2022 |
| Abstract | 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)5- 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)5- is prepared by electrospray ionization, and its reaction with CH3I 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)4(OCCH3)]-, which is formed by successive nucleophilic substitution and reductive elimination, instead of the halogen-bonded complex (XC) CH3-I···Mn(CO)5-, because the I···Mn interaction is weak within XC and it could be a transient species. Inspiringly, DFT calculations predict that replacing CH3I with CF3I 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. |
| Journal | Molecules |
| Volume Number | 27 |
| DOI | 10.3390/molecules27228069 |
| PubMed Central reference number | PMC9692347 |
| Issue Number | 22 |
| PubMed reference number | 36432170 |
| e-ISSN | 14203049 |
| Language | English |
| Publisher | Molecular Diversity Preservation International (MDPI) |
| Publisher Date | 2022-11-21 |
| Access Restriction | Open |
| Subject Keyword | halogen bond metallic anion nucleophilic substitution reaction quantum chemistry calculation reductive elimination |
| Content Type | Text |
| Resource Type | Article |
| Subject | Physical and Theoretical Chemistry Medicine Chemistry Drug Discovery Pharmaceutical Science Analytical Chemistry Molecular Medicine Organic Chemistry |
