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

Abstract

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.

Electronic Structures of Divinylchalcogenophene‐Bridged Biruthenium Complexes: Exploring Trends from O to Te

“…In this regard, the bimetallic complexes [L n M(µ‐bridge)ML n ], in which two ostensibly redox‐active metal centres M supported by auxiliary ligands L are linked by a π‐conjugated bridging unit, have attracted considerable attention , . Consequently, bimetallic complexes featuring a wide variety of metal end‐caps and π‐conjugated bridges, including carbon‐rich chains such as oligoynyl, oligoenyl, aromatic hydrocarbons and heterocycles,, bridging ligands containing other main‐group elements, carboranes and even other metal units, have been prepared and studied.…”

Different Degrees of Electron Delocalization in Mixed Valence Ru‐Ru‐Ru Compounds by Cyanido‐/Isocyanido‐Bridge Isomerism

“…In 2014, Baraldo and co‐workers reported the first example of class III cyanido‐bridged species, which was confirmed by in situ near‐infrared (NIR) and IR spectroscopy and supported by DFT calculations . Recently, we have reported an example of a delocalized cyanide‐bridged MV compound induced by thermal ET . Unfortunately, the molecular structure of this compound was not obtained as isolation and full characterization of cyanido‐bridged MV compounds is challenging.…”

“…[8] Recently,w eh ave reported an example of ad elocalized cyanide-bridged MV compound induced by thermal ET. [9] Unfortunately,t he molecular structure of this compound was not obtained as isolation and full characterization of cyanido-bridged MV compounds is challenging.…”

Different Degrees of Electron Delocalization in Mixed Valence Ru‐Ru‐Ru Compounds by Cyanido‐/Isocyanido‐Bridge Isomerism

“…[2d] Thee nergy of the absorption of class II-III MV compounds is solvent independent, but the charge is localized. [9] Unfortunately,t he molecular structure of this compound was not obtained as isolation and full characterization of cyanido-bridged MV compounds is challenging. [8] Recently,w eh ave reported an example of ad elocalized cyanide-bridged MV compound induced by thermal ET.…”