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- Title
An Unusually Delocalized Mixed-Valence State of a Cyanidometal-Bridged Compound Induced by Thermal Electron Transfer.
- Authors
Ma, Xiao; Lin, Chen ‐ Sheng; Zhu, Xiao ‐ Quan; Hu, Sheng ‐ Min; Sheng, Tian ‐ Lu; Wu, Xin ‐ Tao
- Abstract
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 [FeIII-NC-RuIII-CN-FeII], which is induced by electron transfer from the central RuII to the terminal FeIII in 1[PF6]4, which was confirmed by IR spectroscopy, magnetic data, and EPR and Mössbauer spectroscopy.
- Subjects
HETEROCYCLIC compounds; CHARGE exchange; THERMAL electrons; CYCLOPENTADIENE; INFRARED spectroscopy
- Publication
Angewandte Chemie, 2017, Vol 129, Issue 6, p1627
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.201610855