State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002, P.R. China.
Angew Chem Int Ed Engl. 2017 Feb 1;56(6):1605-1609. doi: 10.1002/anie.201610855. Epub 2017 Jan 12.
The heterometallic complexes trans-[Cp(dppe)FeNCRu(o-bpy)CNFe(dppe)Cp][PF ] (1[PF ] , n=2, 3, 4; o-bpy=1,2-bis(2,2'-bipyridyl-6-yl)ethane, dppe=1,2-bis(diphenylphosphino)ethane, Cp=1,3-cyclopentadiene) in three distinct states have been synthesized and fully characterized. 1 [PF ] and 1 [PF ] are the one- and two-electron oxidation products of 1 [PF ] , respectively. The investigated results suggest that 1[PF ] is a Class II mixed valence compound. 1[PF ] after a thermal treatment at 400 K shows an unusually delocalized mixed valence state of [Fe -NC-Ru -CN-Fe ], which is induced by electron transfer from the central Ru to the terminal Fe in 1[PF ] , which was confirmed by IR spectroscopy, magnetic data, and EPR and Mössbauer spectroscopy.
已合成并充分表征了三种不同状态的偕金属配合物反式-[Cp(dppe)FeNCRu(o-bpy)CNFe(dppe)Cp][PF ](1[PF ], n=2,3,4；o-bpy=1,2-双(2,2'-联吡啶-6-基)乙烷，dppe=1,2-双(二苯基膦)乙烷，Cp=1,3-环戊二烯)。1[PF ]和 1[PF ]分别是 1[PF ]的一价和二价氧化产物。研究结果表明，1[PF ]是一种 II 类混合价态化合物。在 400 K 下进行热处理后，1[PF ]显示出异常离域的混合价态[Fe-NC-Ru-CN-Fe]，这是由 1[PF ]中中心 Ru 向末端 Fe 的电子转移引起的，这一点通过红外光谱、磁性数据以及 EPR 和穆斯堡尔光谱得到了证实。
