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Low-barrier hydrogen bonds and enzymic catalysis

✍ Scribed by Cleland, W.; Kreevoy, M.


Book ID
111918421
Publisher
American Association for the Advancement of Science
Year
1994
Tongue
English
Weight
894 KB
Volume
264
Category
Article
ISSN
0036-8075

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High-level ab initio and DFT molecular orbital calculations have been used to investigate the physical properties of a model low-barrier hydrogen Ž . bond LBHB system: formic acid᎐formate anion. In the gas phase, it is found w that the hydrogen bond formed is extraordinarily short and strong ca. 27

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There are large differences between the acidity of the enol of the acyclic diketone, 2,4-pentanedione and those of two cyclic diketones, 1,3-cyclopentanedione and 1,3-cyclohexanedione. Computational studies have demonstrated that these differences are largely due to the strength of the internal low-