期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 131, 期 37, 页码 13548-13554出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja905806h
关键词
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资金
- NSF [CRE99-82103, CHE03-53091, CHE07-42801, CHE97-09183, CHE-0634989]
- Chungnam National University
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0741968] Funding Source: National Science Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0742801] Funding Source: National Science Foundation
The large pK(a) difference between first and second deprotonations of (+/-)-alpha,alpha'-di-tert-butylsuccinic acid has been interpreted as evidence for a short, strong intramolecular hydrogen bond in the monoanion. Incorporation of (18)O into one carboxyl group allows investigation of the symmetry of the H-bond in solution by the method of isotopic perturbation. Relative to the intrinsic (18)O-induced isotope shift at the carboxyl carbon, as measured in the diacid, an additional isotope shift of 8 ppb in methanol, 14 ppb in acetone, and 5 ppb in THF is observed for potassium hydrogen (+/-)-alpha,alpha'-di-tert-butylsuccinate-(18)O. This increase indicates that the ion exists as an equilibrating pair of interconverting tautomers and not as a single symmetric resonance hybrid. The X-ray crystal structures of the tetrapropylammonium, tetrabutylammonium, tetrabutylphosphonium, magnesium, and calcium hydrogen (+/-)-alpha,alpha'-di-tert-butylsuccinate salts show a remarkably short O-O distance of 2.41 angstrom, consistent with a strong hydrogen bond. However, the dicesium salt of the (+/-)-alpha,alpha'-di-tert-butylsuccinate dianion also shows the short O-O distance of 2.41 angstrom, so this cannot be taken as evidence for a strong hydrogen bond in the monoanion. Moreover, the two O-H distances in the monoanions are unequal, and the hydrogen bond is asymmetric in these crystals. It is concluded that there is no evidence for any special stabilization associated with symmetric H-bonds. The large Delta pK(a) difference is therefore not due to any feature of the H-bond itself but is attributed to the electrostatic repulsion between the carboxylates in the dianion, which is relieved in the monoanion by inserting a proton between the carboxylates.
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