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Application of a Structure/Oxidation-State Correlation to Complexes of Bridging Azo Ligands

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Title Application of a Structure/Oxidation-State Correlation to Complexes of Bridging Azo Ligands
 
Creator DAS, A
SCHERER, TM
MOBIN, SM
KAIM, W
LAHIRI, GK
 
Subject azo compounds
electrochemistry
EPR spectroscopy
noninnocent ligands
ruthenium
TRANSITION-METAL-COMPLEXES
DENSITY-FUNCTIONAL THEORY
INTRAMOLECULAR ELECTRON-TRANSFER
MIXED-VALENCE COMPLEXES
DOT CELLULAR-AUTOMATA
OXIDATION-STATE
DIRUTHENIUM COMPLEX
RADICAL COMPLEXES
ELECTROCHEMICAL PROPERTIES
EXCITATION-ENERGIES
 
Description 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 (dNN) 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)2Ru1(mu-abpy)Ru2(bpy)2](ClO4)2 ([1](ClO4)2), [Ru(acac)2(abpy)] (2), [Ru(bpy)2(abpy)](ClO4)2 ([3](ClO4)2), and meso-[(bpy)2Ru(mu-abpy)Ru(bpy)2](ClO4)3 ([4](ClO4)3; acac-=2,4-pentanedionato, bpy=2,2'-bipyridine). In agreement with DFT calculations, both mononuclear species 2 and 32+ can be described as ruthenium(II) complexes of unreduced abpy0, with 1.295(5)
 
Publisher WILEY-V C H VERLAG GMBH
 
Date 2014-10-16T15:05:00Z
2014-10-16T15:05:00Z
2012
 
Type Article
 
Identifier CHEMISTRY-A EUROPEAN JOURNAL, 18(35)11007-11018
http://dx.doi.org/10.1002/chem.201201049
http://dspace.library.iitb.ac.in/jspui/handle/100/15857
 
Language en