Ambrosio Francesco, Capobianco Amedeo, Landi Alessandro, Pizza Teodoro, Peluso Andrea
Dipartimento di Scienze, Università degli Studi della Basilicata, Viale dell'Ateneo Lucano, 10 - 85100 Potenza (PZ), Italy.
Dipartimento di Chimica e Biologia Adolfo Zambelli, Università di Salerno, Via Giovanni Paolo II, I-84084 Fisciano (SA), Italy.
Phys Chem Chem Phys. 2023 Jan 18;25(3):2359-2365. doi: 10.1039/d2cp05176a.
The mechanism of toluene nitration by NOBF in dichloromethane solution is investigated by performing advanced MD simulations of the reaction trajectories, including at full quantum mechanical level the effects of both the solvent and of the counterion. The time evolution of the encounter complex, as well as that of the associated electronic structure, for different trajectories reveals that a single electron transfer step fastly occurs after reactants are accommodated in a common solvation shell, always preceding the formation of the σ-complex. The present results strongly suggest that the regioselectivity of the reaction is spin-density driven and that a thin mechanism, one based on reaction intermediates and transition states, can be appropriate to describe aromatic nitration.
通过对反应轨迹进行高级分子动力学模拟，研究了在二氯甲烷溶液中由NOBF进行甲苯硝化的机理，其中包括在全量子力学水平上考虑溶剂和抗衡离子的影响。不同轨迹下遭遇复合物的时间演化以及相关电子结构的时间演化表明，在反应物被容纳在共同溶剂化壳层后，单电子转移步骤迅速发生，且总是先于σ-络合物的形成。目前的结果有力地表明，该反应的区域选择性是由自旋密度驱动的，并且基于反应中间体和过渡态的简洁机理可能适合描述芳烃硝化反应。
