Spectroscopy of mixed valent states in dinuclear ions and metalloproteins
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Interacting metal and ligand based open shell systems: Challenges for experiment and theory
2017, Coordination Chemistry ReviewsCitation Excerpt :While all reasonable alternatives for systems Ru-(μ-L)-Ru with di- and trivalent ruthenium appear realized (Scheme 4), there is still potential for such mixed-valent/redox-isomeric arrangements with lower and higher oxidation states. Some donor-bridged RuIVRuIII mixed-valent species such as oxamido-coupled systems (Scheme 11) have been reported and analyzed [31a], whereas RuIIRuI intermediates are truly rare [4d] (Scheme 11), requiring an easily reduced acceptor bridge like 2,2′-azobipyridine [12a,33b] and co-ligands which stabilize low oxidation states. In each case of Scheme 11 the experimental IVCT absorption in the near infrared and the DFT calculated electronic structures confirm the mixed-valent character.
Mixed valency of a 5d element: The osmium example
2013, Coordination Chemistry ReviewsCitation Excerpt :The 3d element compounds can present some experimental difficulties due to their labile bonding to common non-chelate ligands and because of the variable spin states, however, both these formidable challenges can be dealt with by using sophisticated ligands in molecules, clusters, or coordination polymers, and by taking advantage of high spin situations in the form of double exchange [16] or valence tautomerism/spin crossover [17] phenomena. The 4d systems do not normally exhibit coordinative lability or spin isomerism which has contributed to the popularity especially of ruthenium compounds in that area [10–14]. This element adopts two inert neighbouring oxidation states (+III, +II), involving an otherwise not very common 4d5 configuration.
Concepts for metal complex chromophores absorbing in the near infrared
2011, Coordination Chemistry Reviewsμ-1,2,4,5-Tetrazine-N<sup>1</sup>:N<sup>4</sup>-bis(pentaammineruthenium) tetracation: Synthesis and X-ray structure
2007, Inorganica Chimica ActaMixed valency in ruthenium complexes-Coordinative aspects
2007, Coordination Chemistry Reviews