论文部分内容阅读
用LCAO分子轨道理论对分子氮络合物的化学键作了处理,得到了能级、电荷密度和键序的表达式。根据能级,讨论了稳定性和金属价态、电子租态d_n的关系;指出单核低价络合物,d~(4-6)最稳定,高价络合物,d~(0-2)稳定。根据电荷密度和键序,分析了电子能谱和红外光谱数据,讨论了还原的可能途径。指出单核高阶态d~(0-2)络合物,较易于发生还原性的亲核反应;低价d~(4-6)络合物将发生亲电子反应,但必须借助EDA型配位体或光激发过程进—步提高N的负电荷密度。双核络合物与单核络合物,结论大致相仿。
The chemical bond of molecular nitrogen complex was treated by LCAO molecular orbital theory, and the expressions of energy level, charge density and bond order were obtained. According to the energy level, we discuss the relationship between the stability and the valence state of the metal and electron rent d_n. It is pointed out that mononuclear low valent complexes, d ~ (4-6) are the most stable and expensive complexes, d ~ (0-2 )stable. Based on the charge density and bond order, the electron and infrared spectra were analyzed, and the possible ways of reduction were discussed. It is pointed out that the mononuclear higher order d ~ (0-2) complex is more prone to the reductive nucleophilic reaction. The electrophilic reaction of the lower d ~ (4-6) complex will occur, but EDA The bit or photoexcitation process further increases the negative charge density of N. Binuclear complexes and mononuclear complexes, the conclusion is broadly similar.