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Experimental and DFT Evidence for the Fractional Non-Innocence of a beta-Diketonate Ligand

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Title Experimental and DFT Evidence for the Fractional Non-Innocence of a beta-Diketonate Ligand
 
Creator DAS, A
SCHERER, TM
MONDAL, P
MOBIN, SM
KAIM, W
LAHIRI, GK
 
Subject density functional calculations
EPR spectroscopy
non-innocent ligands
ruthenium
X-ray diffraction
DENSITY-FUNCTIONAL THEORY
BRIDGING LIGAND
REDOX SERIES
RUTHENIUM(III) COMPLEXES
DIRUTHENIUM COMPLEX
EXCITATION-ENERGIES
TRANSITION-METAL
STATE ANALYSIS
MOLECULES
CHEMISTRY
 
Description New compounds [Ru(pap)2(L)](ClO4), [Ru(pap)(L)2], and [Ru(acac)2(L)] (pap=2-phenylazopyridine, L-=9-oxidophenalenone, acac-=2,4-pentanedionate) have been prepared and studied regarding their electron-transfer behavior, both experimentally and by using DFT calculations. [Ru(pap)2(L)](ClO4) and [Ru(acac)2(L)] were characterized by crystal-structure analysis. Spectroelectrochemistry (EPR, UV/Vis/NIR), in conjunction with cyclic voltammetry, showed a wide range of about 2 V for the potential of the RuIII/II couple, which was in agreement with the very different characteristics of the strongly p-accepting pap ligand and the s-donating acac- ligand. At the rather high potential of +1.35 V versus SCE, the oxidation of L- into L. could be deduced from the near-IR absorption of [RuIII(pap)(L.)(L-)]2+. Other intense long-wavelength transitions, including LMCT (L-?RuIII) and LL/CT (pap.-?L-) processes, were confirmed by TD-DFT results. DFT calculations and EPR data for the paramagnetic intermediates allowed us to assess the spin densities, which revealed two cases with considerable contributions from L-radical-involving forms, that is, [RuIII(pap0)2(L-)]2+?[RuII(pap0)2(L.)]2+ and [RuIII(pap0)(L-)2]+?[RuII(pap0)(L center dot)(L-)]+. Calculations of electrogenerated complex [RuII(pap.-)(pap0)(L-)] displayed considerable negative spin density (-0.188) at the bridging metal.
 
Publisher WILEY-V C H VERLAG GMBH
 
Date 2014-10-16T15:04:30Z
2014-10-16T15:04:30Z
2012
 
Type Article
 
Identifier CHEMISTRY-A EUROPEAN JOURNAL, 18(45)14434-14443
http://dx.doi.org/10.1002/chem.201201785
http://dspace.library.iitb.ac.in/jspui/handle/100/15856
 
Language en