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- W4292367167 abstract "Abstract A comparison of computed 19 F NMR chemical shifts and experiment provides evidence for large specific solvent effects for fluoride‐type anions interacting with the σ*(C−H) orbitals in organic solvents like MeCN or CH 2 Cl 2 . We show this for systems ranging from the fluoride ion and the bifluoride ion [FHF] − to polyhalogen anions [ClF x ] − . Discrepancies between computed and experimental shifts when using continuum solvent models like COSMO or force‐field‐based descriptions like the 3D‐RISM‐SCF model show specific orbital interactions that require a quantum‐mechanical treatment of the solvent molecules. This is confirmed by orbital analyses of the shielding constants, while less negatively charged fluorine atoms (e. g., in [EF 4 ] − ) do not require such quantum‐mechanical treatments to achieve reasonable accuracy. The larger 19 F solvent shift of fluoride in MeCN compared to water is due to the larger coordination number in the former. These observations are due to unusually strong charge‐assisted C−H⋅⋅⋅F − hydrogen bonds, which manifest beyond some threshold negative natural charge on fluorine of ca. < −0.6 e. The interactions are accompanied by sizable free energies of solvation, in the order F − ≫[FHF] − >[ClF 2 ] − >[ClF 4 ] − . COSMO‐RS solvation free energies tend to moderately underestimate those from the micro‐solvated cluster treatment. Red‐shifted and intense vibrational C−H stretching bands, potentially accessible in bulk solution, are further spectroscopic finger prints." @default.
- W4292367167 created "2022-08-20" @default.
- W4292367167 creator A5032199290 @default.
- W4292367167 creator A5062903559 @default.
- W4292367167 creator A5069158812 @default.
- W4292367167 creator A5089111876 @default.
- W4292367167 date "2022-08-19" @default.
- W4292367167 modified "2023-10-14" @default.
- W4292367167 title "Unusually Large Effects of Charge‐assisted C−H⋅⋅⋅F Hydrogen Bonds to Anionic Fluorine in Organic Solvents: Computational Study of <sup>19</sup>F NMR Shifts versus Thermochemistry" @default.
- W4292367167 cites W1528130557 @default.
- W4292367167 cites W182601290 @default.
- W4292367167 cites W1913750538 @default.
- W4292367167 cites W1972776152 @default.
- W4292367167 cites W1977351611 @default.
- W4292367167 cites W1982263362 @default.
- W4292367167 cites W1982356449 @default.
- W4292367167 cites W1986816653 @default.
- W4292367167 cites W1987824072 @default.
- W4292367167 cites W1988091937 @default.
- W4292367167 cites W1989736310 @default.
- W4292367167 cites W1992116408 @default.
- W4292367167 cites W1993077801 @default.
- W4292367167 cites W1995535745 @default.
- W4292367167 cites W1996954258 @default.
- W4292367167 cites W1999578292 @default.
- W4292367167 cites W1999913247 @default.
- W4292367167 cites W2000576273 @default.
- W4292367167 cites W2007502740 @default.
- W4292367167 cites W2012866556 @default.
- W4292367167 cites W2015221035 @default.
- W4292367167 cites W2015570651 @default.
- W4292367167 cites W2016412681 @default.
- W4292367167 cites W2018062902 @default.
- W4292367167 cites W2018113064 @default.
- W4292367167 cites W2018674598 @default.
- W4292367167 cites W2021658339 @default.
- W4292367167 cites W2022366997 @default.
- W4292367167 cites W2023271753 @default.
- W4292367167 cites W2024095548 @default.
- W4292367167 cites W2030687437 @default.
- W4292367167 cites W2033834998 @default.
- W4292367167 cites W2034516186 @default.
- W4292367167 cites W2034779428 @default.
- W4292367167 cites W2036431015 @default.
- W4292367167 cites W2038767330 @default.
- W4292367167 cites W2039841285 @default.
- W4292367167 cites W2041321352 @default.
- W4292367167 cites W2042239753 @default.
- W4292367167 cites W2043668344 @default.
- W4292367167 cites W2044240337 @default.
- W4292367167 cites W2044711915 @default.
- W4292367167 cites W2046960330 @default.
- W4292367167 cites W2049364454 @default.
- W4292367167 cites W2053845743 @default.
- W4292367167 cites W2054164390 @default.
- W4292367167 cites W2054740178 @default.
- W4292367167 cites W2055563809 @default.
- W4292367167 cites W2057359450 @default.
- W4292367167 cites W2058065178 @default.
- W4292367167 cites W2058200314 @default.
- W4292367167 cites W2060043202 @default.
- W4292367167 cites W2065540974 @default.
- W4292367167 cites W2065809333 @default.
- W4292367167 cites W2069006374 @default.
- W4292367167 cites W2070203126 @default.
- W4292367167 cites W2074584890 @default.
- W4292367167 cites W2074796643 @default.
- W4292367167 cites W2078511427 @default.
- W4292367167 cites W2079280953 @default.
- W4292367167 cites W2081068731 @default.
- W4292367167 cites W2082324237 @default.
- W4292367167 cites W2083173159 @default.
- W4292367167 cites W2086957099 @default.
- W4292367167 cites W2087141492 @default.
- W4292367167 cites W2092035185 @default.
- W4292367167 cites W2092157292 @default.
- W4292367167 cites W2096747776 @default.
- W4292367167 cites W2098455988 @default.
- W4292367167 cites W2101755468 @default.
- W4292367167 cites W2105044776 @default.
- W4292367167 cites W2116373706 @default.
- W4292367167 cites W2119547517 @default.
- W4292367167 cites W2125794794 @default.
- W4292367167 cites W2126131886 @default.
- W4292367167 cites W2132795750 @default.
- W4292367167 cites W2139335926 @default.
- W4292367167 cites W2143772867 @default.
- W4292367167 cites W2146798438 @default.
- W4292367167 cites W2150345533 @default.
- W4292367167 cites W2156115804 @default.
- W4292367167 cites W2165958678 @default.
- W4292367167 cites W2167996954 @default.
- W4292367167 cites W2254478395 @default.
- W4292367167 cites W2282896843 @default.
- W4292367167 cites W2299621452 @default.
- W4292367167 cites W2321463950 @default.
- W4292367167 cites W2322826137 @default.
- W4292367167 cites W2323800439 @default.
- W4292367167 cites W2324014950 @default.
- W4292367167 cites W2329845354 @default.