Universidad Andrés Bello, Facultad de Ciencias Exactas, Departamento de Ciencias Químicas, Centro de Química Teórica & Computacional (CQT&C), Avenida República 275, 8370146, Santiago de Chile., Chile.
Universidad de Córdoba, Facultad de Ciencias Básicas, Grupo de Química Computacional., Carrera 6 No., 77-305, Montería, Córdoba, Colombia.
Chemphyschem. 2023 Jun 1;24(11):e202200867. doi: 10.1002/cphc.202200867. Epub 2023 Mar 23.
In this study, we revealed the significance of chemical bonding for the photochemically induced mechanism of 2-phenyl tetrazole derivatives generating nitrile imines. The correlated electron localization function shows that the formation of imine nitrile involves two key bond events: (i) the heterolytic C-N breakage taking place in the T state and (ii) the homolytic N-N rupture occurring in the T excited state. In particular, a cation-radical specie results from the C-N cleavage, whereas the N-N rupture creates a biradical resonant form of imine nitrile. Additionally, we noticed that the substantial pair delocalization of the C-C-N bonded structure could play a significant role in the conversion of the biradical imine nitrile into both the propargylic and allenic forms via the T →S deactivation.
在这项研究中，我们揭示了化学成键对于 2-苯基四唑衍生物生成腈亚胺的光化学反应机制的重要性。相关的电子定域函数表明，亚胺腈的形成涉及两个关键的键事件：（i）在 T 态下发生的异裂 C-N 断裂，以及（ii）在 T 激发态下发生的均裂 N-N 断裂。特别是，C-N 断裂产生了正碳离子自由基，而 N-N 断裂则产生了亚胺腈的双自由基共振形式。此外，我们注意到，C-C-N 键合结构的大量电子离域可能在 T→S 去活化过程中通过 T 态转化为丙炔基和烯丙基形式的双自由基亚胺腈中发挥重要作用。
