An Unusually Delocalized Mixed-Valence State of a Cyanidometal-Bridged Compound Induced by Thermal Electron Transfer

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• 作者：Dr. Xiao Ma ; Dr. Chen-Sheng Lin ; Dr. Xiao-Quan Zhu ; Sheng-Min Hu ; Prof. Dr. Tian-Lu Sheng and Prof. Xin-Tao Wu
• 刊名：Angewandte Chemie International Edition
• 出版年：2017
• 出版时间：February 1, 2017
• 年：2017
• 卷：56
• 期：6
• 页码：1605-1609
• 全文大小：1382K
• ISSN：1521-3773

文摘

The heterometallic complexes trans-[Cp(dppe)FeNCRu(o-bpy)CNFe(dppe)Cp][PF₆]_n (1[PF₆]_n, 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. 1³⁺[PF₆]₃ and 1⁴⁺[PF₆]₄ are the one- and two-electron oxidation products of 1²⁺[PF₆]₂, respectively. The investigated results suggest that 1[PF₆]₃ is a Class II mixed valence compound. 1[PF₆]₄ after a thermal treatment at 400 K shows an unusually delocalized mixed valence state of [Fe^III-NC-Ru^III-CN-Fe^II], which is induced by electron transfer from the central Ru^II to the terminal Fe^III in 1[PF₆]₄, which was confirmed by IR spectroscopy, magnetic data, and EPR and Mössbauer spectroscopy.