The seeming lack of CF center dot center dot center dot HO intramolecular hydrogen bonds in linear aliphatic fluoroalcohols in solution

作者：Cormanich R A; Rittner R; Freitas M P^*; Buehl M

来源：Physical Chemistry Chemical Physics, 2014, 16(36): 19212-19217.

DOI：10.1039/c4cp02463j

No CF center dot center dot center dot HO intramolecular hydrogen bonds (IHBs) in 2-fluoroethanol, 3-fluoropropanol and 4-fluorobutanol can be detected experimentally in solution by NMR and infrared spectroscopies. According to ab initio (MP2/aug-cc-pVDZ) and DFT calculations (B3LYP), a CF center dot center dot center dot HO IHB has no influence on the conformational behavior of 2-fluoroethanol, while it stabilises the global minima of 3-fluoropropanol and 4-fluorobutanol for the isolated molecules. Entropy and bulk salvation effects, even in nonpolar media, such as CCl4, cyclohexane and dichloromethane, are indicated to diminish the population of these global minima, apparently below the detection limit.

• 出版日期2014