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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Effect of a Heteroatom on Bonding Patterns and Triradical Stabilization Energies of 2,4,6-Tridehydropyridine versus 1,3,5-Tridehydrobenzene
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Effect of a Heteroatom on Bonding Patterns and Triradical Stabilization Energies of 2,4,6-Tridehydropyridine versus 1,3,5-Tridehydrobenzene

机译：杂原子对2,4,6-三氢吡啶与1,3,5-三氢吡啶键的键合模式和三基稳定能的影响

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摘要

Electronic structure of 2,4,6-tridehydropyridine and isoelectronic 1,3,5-tridehydrobenzene is characterized by the equation-of-motion spin-flip coupled-cluster calculations with single and double substitutions and including perturbative triple corrections. Equilibrium geometries of the three lowest electronic states, vertical and adiabatic states ordering, and triradical stabilization energies are reported for both triradicals. In 1,3,5-tridehydrobenzene, the ground 2A1 state is 0.016 eV below the 2B2 state, whereas in 2,4,6-tridehydropyridine the heteroatom reverses adiabatic state ordering bringing 2B2 below 2A1 by 0.613 eV. The doublet-quartet gap is also larger in 2,4,6-tridehydropyridine as compared to 1,3,5-tridehydrobenzene; the respective adiabatic values are 1.223 and 0.277 eV. Moreover, the heteroatom reduces bonding interactions between the C2 and C6 radical centers, which results in the increased stabilizing interactions between C4 and C2/C6. Triradical stabilization energies corresponding to the separation of C4 and C2 are 19.7 and -0.2 kcal/mol, respectively,in contrast to 2.8 kcal/mol in 1,3,5-tridehydrobenzene. Similarly weak interactions between C2 and C6 are also observed in 2,6-didehydropyridine resulting in a nearly zero singlet-triplet energy gap, in contrast to m-benzyne and 2,4-didehydropyridine. The total interaction energy of the three radical centers is very similar in 1,3,5-tridehydrobenzene and 2,4,6-tridehydropyridine and is 19.5 and 20.1 kcal/mol, respectively.
机译：2,4,6-三氢吡啶和等电子1,3,5-三氢吡啶的电子结构的特征在于运动方程式的自旋翻转耦合簇计算，具有单取代和双取代，包括扰动三重校正。报告了两个三基态的三个最低电子态的平衡几何形状，垂直和绝热态有序性以及三基态稳定能。在1,3,5-叔丁基氢苯中，基态2A1比2B2态低0.016 eV，而在2,4,6-叔丁基氢吡啶中，杂原子逆转绝热状态，使2B2在2A1之下低0.613 eV。与1,3,5-叔丁基氢苯相比，2,4,6-叔丁基氢吡啶中的四重峰-四重峰间隙也更大;各自的绝热值为1.223和0.277 eV。而且，杂原子减少了C2和C6自由基中心之间的键相互作用，这导致C4和C2 / C6之间的稳定相互作用增加。与C4和C2的分离相对应的三基稳定能分别为19.7和-0.2 kcal / mol，而在1,3,5-三氢苯中则为2.8 kcal / mol。类似地，在2，6-二氢吡啶中也观察到C2和C6之间的弱相互作用，与间苯并和2，4-二氢吡啶相比，导致几乎为零的单重态-三重态能隙。三个自由基中心的总相互作用能在1,3,5-叔丁基氢吡啶和2,4,6-叔丁基氢吡啶中非常相似，分别为19.5和20.1 kcal / mol。

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