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Application of a structure/oxidation-state correlation to complexes of bridging azo ligands
Amit Das1, Thomas Michael Scherer, Shaikh M Mobin
1Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, India.
Abstract:
Based on data from more than 40 crystal structures of metal complexes with azo-based bridging ligands (2,2'-azobispyridine, 2,2'-azobis(5-chloropyrimidine), azodicarbonyl derivatives), a correlation between the N-N bond lengths (d(NN)) and the oxidation state of the ligand (neutral, neutral/back-donating, radical-anionic, dianionic) was derived. This correlation was applied to the analysis of four ruthenium compounds of 2,2'-azobispyridine (abpy), that is, the new asymmetrical rac-[(acac)(2)Ru1(μ-abpy)Ru2(bpy)(2)](ClO(4))(2) ([1](ClO(4))(2)), [Ru(acac)(2)(abpy)] (2), [Ru(bpy)(2)(abpy)](ClO(4))(2) ([3](ClO(4))(2)), and meso-[(bpy)(2)Ru(μ-abpy)Ru(bpy)(2)(ClO(4))(3) ([4](ClO(4))(3); acac(-) =2,4-pentanedionato, bpy=2,2'-bipyridine). In agreement with DFT calculations, both mononuclear species 2 and 3(2+) can be described as ruthenium(II) complexes of unreduced abpy(0), with 1.295(5)
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