Shen Guang-Bin, Qian Bao-Chen, Luo Guang-Ze, Fu Yan-Hua, Zhu Xiao-Qing
School of Medical Engineering, Jining Medical University, Jining, Shandong 272000, P. R. China.
College of Chemistry and Environmental Engineering, Anyang Institute of Technology, Anyang, Henan 455000, China.
ACS Omega. 2023 Aug 21;8(35):31984-31997. doi: 10.1021/acsomega.3c03804. eCollection 2023 Sep 5.
Since the hydrogenation of imines (X) and the dehydrogenation of amines (XH) generally involve the two hydrogen ions (H + H) transfer, the thermodynamic abilities of various amines releasing hydrides or two hydrogen ions as well as various imines accepting protons or two hydrogen ions are important and characteristic physical parameters. In this work, the p values of 84 protonated imines (XH) in acetonitrile were predicted. Combining Gibbs free energy changes of amines releasing hydrides in acetonitrile from our previous work with the p(XH) values, the Gibbs free energy changes of amines releasing two hydrogen ions and imines accepting two hydrogen ions were derived using Hess's law by constructing thermochemical cycles, and the thermodynamic evaluations of amines as hydrides or two hydrogen ions reductants and imines as protons or two hydrogen ions acceptors are well compared and discussed. Eventually, the practical application of thermodynamic data for amines and imines on hydrogenation feasibility, mechanism, and possible elementary steps was shown and discussed in this paper from the point of thermodynamics.
由于亚胺（X）的氢化和胺（XH）的脱氢通常涉及两个氢离子（H + H）的转移，因此各种胺释放氢化物或两个氢离子以及各种亚胺接受质子或两个氢离子的热力学能力是重要且具有特征性的物理参数。在这项工作中，预测了84种质子化亚胺（XH）在乙腈中的p值。将我们之前工作中胺在乙腈中释放氢化物的吉布斯自由能变化与p（XH）值相结合，利用赫斯定律通过构建热化学循环推导了胺释放两个氢离子和亚胺接受两个氢离子的吉布斯自由能变化，并对胺作为氢化物或两个氢离子还原剂以及亚胺作为质子或两个氢离子受体的热力学评估进行了很好的比较和讨论。最终，本文从热力学角度展示并讨论了胺和亚胺的热力学数据在氢化可行性、机理和可能的基元步骤方面的实际应用。
