Hydrogen Bonded Arrays: The Power of Multiple Hydrogen Bonds

被引：64

作者：

Shokri, Alireza ^{[2
]}

Schmidt, Jacob ^{[2
]}

Wang, Xue-Bin ^{[1
,3
]}

Kass, Steven R. ^{[2
]}

机构：

[1] Pacific NW Natl Lab, Div Chem & Mat Sci, Richland, WA 99352 USA

[2] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA

[3] Washington State Univ, Dept Phys, Richland, WA 99354 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 04期

基金：

美国国家科学基金会;

关键词：

PHOTOELECTRON-SPECTROSCOPY; DENSITY FUNCTIONALS; OXYANION HOLE; PROTON ABSTRACTION; CATALYTIC TRIAD; CARBON ACIDS; CROWN-ETHERS; ACTIVE-SITE; BASIS-SETS; ENERGETICS;

D O I：

10.1021/ja2081907

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Hydrogen bond interactions in small covalent model compounds (i.e., deprotonated polyhydroxy alcohols) were measured by negative ion photoelectron spectroscopy. The experimentally determined vertical and adiabatic electron detachment energies for (HOCH2CH2)(2)CHO- (2a), (HOCH2CH2)(3)CO- (3a), and (HOCH2CH2CH(OH)CH2)(3)CO- (4a) reveal that hydrogen-bonded networks can provide enormous stabilizations and that a single charge center not only can be stabilized by up to three hydrogen bonds but also can increase the interaction energy between noncharged OH groups by 5.8 kcal mol(-1) or more per hydrogen bond. This can lead to pK(a) values that are very different from those in water and can provide some of the impetus for catalytic processes.

引用

页码：2094 / 2099

页数：6

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