Departamento de Química Orgánica y Centro de Innovación en Química Avanzada (ORFEO-CINQA) Facultad de Ciencias Químicas, Universidad Complutense de Madrid Ciudad Universitaria, 28040-, Madrid, Spain.
Chemistry. 2023 Jun 13;29(33):e202300577. doi: 10.1002/chem.202300577. Epub 2023 Apr 27.
The poorly understood factors governing the small molecule activation reactions mediated by diazaborinines have been computationally explored in detail using quantum chemical tools. To this end, the activation of E-H σ-bonds (E = H, C, Si, N, P, O, S) has been investigated. These reactions, which proceed in a concerted manner, are exergonic and, in general, associated with relatively low activation barriers. In addition, the barrier becomes lower for the E-H bonds involving the heavier element in the same group (ΔG : C>Si; N>P; O>S). This reactivity trend together with the mode of action of the diazaborinine system are quantitatively analyzed by means of the activation strain model of reactivity in combination with the energy decomposition analysis method.
使用量子化学工具详细探讨了由二氮硼烷介导的小分子激活反应的控制因素，这些反应以协同的方式进行，是放能的，通常与相对较低的活化能垒有关。此外，对于同一族中涉及较重元素的 E-H 键（ΔG：C>Si；N>P；O>S），其能垒会降低。这种反应活性趋势以及二氮硼烷系统的作用模式，通过反应活性的应变模型与能量分解分析方法相结合进行了定量分析。
