Zhang Zheng-Feng, Su Ming-Der
Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan.
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 80708, Taiwan.
Inorg Chem. 2023 Aug 21;62(33):13315-13327. doi: 10.1021/acs.inorgchem.3c01611. Epub 2023 Aug 7.
The emission of SO gas by industrialized societies contributes to the occurrence of acid rain in natural environments. In this study, we put forward a theoretical investigation into the capture reactions of SO. Our analysis centers on the energy profiles of intramolecular 1,2-cyclohexylene-bridged FLP-associated molecules. We will particularly examine the reactions involving G13/P-based (with G13 denoting Group 13 element) and B/G15-based (with G15 representing Group 15 element) FLP-associated molecules. Except for Tl/P-FLP, B/N-FLP, and B/Bi-FLP, our theoretical examinations indicate that the remaining six FLP-associated molecules, namely G13'/P-FLP (G13' = B, Al, Ga, and In) and B/G15 ' -FLP (G15' = P, As, and Sb), can easily undergo SO capture reactions due to their energetic feasibility. Particularly, our theoretical findings suggested that 1,2-cyclohexylene-bridged Al/P-FLP, Ga/P-FLP, B/As-FLP, and B/Sb-FLP are capable of undergoing a reversible reaction and returning to the initial reactant state. Our theoretical evidence indicates that the G13-G15 bond length in the 1,2-cyclohexylene-linked G13/G15-FLP can serve as a basis for evaluating the free activation barrier associated with its reaction with SO. Two theoretical methods, namely, the frontier molecular orbital theory and the energy decomposition analysis-natural orbitals of chemical valence approach, are utilized to investigate the electronic structure and bonding nature of the reactions under consideration. Moreover, the analyses based on the activation strain model revealed that it is the geometrical deformation energies of G13/G15-FLP, which is the key factor that greatly influences the activation barriers of such SO capture reactions. Further, our theoretical computations indicate that such capturing reactions of SO by intramolecular 1,2-cyclohexylene-linked G13/G15-based FLP-type molecules obey the Hammond postulate.
工业化社会排放的二氧化硫气体导致了自然环境中酸雨的出现。在本研究中，我们对二氧化硫的捕获反应进行了理论研究。我们的分析集中在分子内1,2 - 亚环己基桥连的FLP相关分子的能量分布上。我们将特别研究涉及基于G13/P（其中G13表示第13族元素）和基于B/G15（其中G15表示第15族元素）的FLP相关分子的反应。除了Tl/P - FLP、B/N - FLP和B/Bi - FLP外，我们的理论研究表明，其余六种FLP相关分子，即G13'/P - FLP（G13' = B、Al、Ga和In）和B/G15' - FLP（G15' = P、As和Sb），由于其能量上的可行性，能够容易地发生二氧化硫捕获反应。特别是，我们的理论研究结果表明，1,2 - 亚环己基桥连的Al/P - FLP、Ga/P - FLP、B/As - FLP和B/Sb - FLP能够发生可逆反应并回到初始反应物状态。我们的理论证据表明，1,2 - 亚环己基连接的G13/G15 - FLP中的G13 - G15键长可作为评估其与二氧化硫反应相关的自由活化能垒的基础。我们采用了两种理论方法，即前线分子轨道理论和能量分解分析 - 化学价自然轨道方法，来研究所考虑反应的电子结构和键合性质。此外，基于活化应变模型的分析表明，G13/G15 - FLP的几何变形能是极大影响此类二氧化硫捕获反应活化能垒的关键因素。进一步地，我们的理论计算表明，分子内1,2 - 亚环己基连接的基于G13/G15的FLP型分子对二氧化硫的此类捕获反应遵循哈蒙德假说。
