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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Modeling Proton-Bound Methanol, Ammonia, and Amine Complexes of 12-Crown-4-Ether and Dimethoxyethane ('Glyme') Using Density Functional Theory
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Modeling Proton-Bound Methanol, Ammonia, and Amine Complexes of 12-Crown-4-Ether and Dimethoxyethane ('Glyme') Using Density Functional Theory

机译：使用密度泛函理论对12冠4醚和二甲氧基乙烷（“甘醇二甲醚”）的质子结合甲醇，氨和胺配合物进行建模

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摘要

The association reactions undergone by 12-crown-4-ether, 12c4H~+, with NH_3, CH_3OH, CH_3NH_2, (CH_3)_2NH, and (CH_3)_3N have been studied using the B3LYP density functional method and a variety of basis sets. For comparison purposes the insertion reactions for the same bases into protonated dimethoxyethane ("glyme"), Gl·H~+, and protonated glyme dimer, (Gl)_2H~+, have also been modeled. The B3LYP/aug-cc-pVDZ//B3LYP/4-21G(~*) level of theory was found to be a particularly favorable compromise between accuracy and computational expense for the calculation of proton affinities of medium-sized species. The protonated glyme, Gl·H~+, the protonated glyme dimer, (Gl)_2H~+, and the protonated crown ether, 12c4H~+, form two internal hydrogen bonds with NH_3, CH_3OH, CH_3NH_2, and (CH_3)_2NH, except for (Gl)_2H~+·NH_3 which has four O…H bonds, In Gl·NH(CH_3)_3~+, there is a single O…H bond and the protons of the methyl groups assist weakly in O…HC bonding. The insertion energy of methanol, ammonia, and the series of amines into 12c4H~+ increases with increasing proton affinity of the inserting base. A similar trend is observed for insertion into (Gl)_2H~+. Trimethylamine does not follow the expected trend because it forms proton-bound complexes that have a single O…HN bond instead of two. The association energy of CH_3OH_2~+, NH_4~+, etc., with 12c4 or Gl_2 decreases with increasing proton affinity (of methanol, ammonia, etc.).
机译：使用B3LYP密度泛函方法和各种基础集研究了12冠4醚12c4H〜+与NH_3，CH_3OH，CH_3NH_2，（CH_3）_2NH和（CH_3）_3N发生的缔合反应。为了进行比较，还对相同碱基插入质子化二甲氧基乙烷（“ glyme”）G1·H〜+和质子化甘醇二糖二聚体（Gl）_2H〜+中的插入反应进行了建模。发现B3LYP / aug-cc-pVDZ // B3LYP / 4-21G（〜*）的理论水平在计算中型物种的质子亲和力的准确性和计算费用之间是一个特别有利的折衷方案。质子化的Gl·H〜+，质子化的二聚体（Gl）_2H〜+和质子化的冠醚12c4H〜+与NH_3，CH_3OH，CH_3NH_2和（CH_3）_2NH形成两个内部氢键，除了（Gl）_2H〜+·NH_3具有四个O…H键外，在Gl·NH（CH_3）_3〜+中，只有一个O…H键，甲基质子对O…HC的辅助作用较弱。粘接。甲醇，氨和一系列胺向12c4H〜+的插入能随着插入碱的质子亲和力的增加而增加。对于插入（G1）_2H〜+中观察到类似的趋势。三甲胺没有遵循预期的趋势，因为它形成的质子结合复合物具有单个O…HN键而不是两个。 CH_3OH_2〜+，NH_4〜+等与12c4或Gl_2的缔合能随着质子亲合力（甲醇，氨等）的增加而降低。

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