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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Gas-phase reactivity of 2,7-dimethyl-[1,2,4]-triazepine thio derivatives toward Cu+ cation: A DFT study
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Gas-phase reactivity of 2,7-dimethyl-[1,2,4]-triazepine thio derivatives toward Cu+ cation: A DFT study

机译：DFT研究表明2,7-二甲基-[1,2,4]-三氮杂硫代衍生物对Cu +阳离子的气相反应性

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摘要

The gas-phase interactions of 2,7-dimethyl-[1,2,4]-triazepine and its thio derivatives with Cu+ were studied through the use of high-level density functional theory (DFT) calculations. The structure of all possible tautomers and their conformers was optimized at the B3LYP/6-31G(d) level of theory. Final energies were obtained at the B3LYP/6-311+G(2df,2p) level. It has been found that the direct association of Cu+ occurs at the oxygen atom attached to position 3 in the case of the dioxo derivative and at the sulfur atom in all other cases. For the dithio derivatives, the global minimum of the PES corresponds to the structure in which the metal ion bridges between the heteroatom at position 3 and the nitrogen atom at position 4 of the corresponding enolic tautomer, forming a four-membered ring structure; for the dioxo derivative, this conformer competes with the ketone tautomer. Moreover, the isomerization processes leading from the most stable adduct to the other stable conformers were investigated. Among all the considered compounds, the 3,5-dithiotriazepines-Cu+ is found to be the one that associates Cu+ more tightly in the gas phase. The calculated Cu+ binding energies show a good correlation with the experimental proton affinities.
机译：通过使用高级密度泛函理论（DFT）计算，研究了2,7-二甲基-[1,2,4]-三氮杂pine及其硫代衍生物与Cu +的气相相互作用。在B3LYP / 6-31G（d）的理论水平上优化了所有可能的互变异构体及其构象异构体的结构。最终能量在B3LYP / 6-311 + G（2df，2p）水平获得。已经发现，在二氧代衍生物的情况下，Cu +的直接缔合发生在连接于位置3的氧原子上，而在所有其他情况下，发生在硫原子上。对于二硫代衍生物，PES的整体最小值对应于这样的结构，其中金属离子在相应烯醇互变异构体的位置3的杂原子和位置4的氮原子之间桥接，形成四元环结构;对于二氧杂衍生物，该构象异构体可与酮互变异构体竞争。此外，研究了从最稳定的加合物到其他稳定构象异构体的异构化过程。在所有考虑的化合物中，发现3,5-二硫代三氮杂卓-Cu +是在气相中与Cu +紧密结合的化合物。计算出的Cu +结合能显示出与实验质子亲和力的良好相关性。

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