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Valence-state analysis through spectroelectrochemistry in a series of quinonoid-bridged diruthenium complexes [(acac)(2)ru(mu-l)ru(acac)(2)](n) (n =+2,+1, 0,-1,-2)

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Title Valence-state analysis through spectroelectrochemistry in a series of quinonoid-bridged diruthenium complexes [(acac)(2)ru(mu-l)ru(acac)(2)](n) (n =+2,+1, 0,-1,-2)
 
Creator GHUMAAN, S
SARKAR, B
MAJI, S
PURANIK, VG
FIEDLER, J
URBANOS, FA
JIMENEZ-APARICIO, R
KAIM, W
LAHIRI, GK
 
Subject magnetic properties
quinones
ruthenium
spectroelectrochemistry
structure elucidation
valence-state distributions
transition-metal-complexes
magnetic exchange interactions
dinuclear ruthenium complexes
charge-transfer ivct
intervalence electron-transfer
mixed-valence
crystal-structures
molecular-structure
chloranilic acid
redox properties
 
Description The quinonoid ligand-bridged diruthenium compounds [(acac)(2)Ru(mu-L(2-))Ru(acac)(2)] (acac(-) = acetylacetonato = 2,4-pentanedionato; L(2-) = 2,5-dioxido-1,4-benzoquinone, 1; 3,6-dichloro-2,5-dioxido-1,4-benzoquinone, 2; 5,8-dioxido-1,4-naphthoquinone, 3; 2-3-dichloro-5,8-dioxido-1,4-naphthoquinone, 4; 1,5-dioxido-9,10-anthraquinone, 5; and 1,5-diimido-9,10-anthraquinone, 6) were prepared and characterized analytically. The crystal structure analysis of 5 in the rac configuration reveals two tris(2,4-pentanedionato)ruthenium moieties with an extended anthracenedione-derived bis(ketoenolatee) pi-conjugated bridging ligand. The weakly antiferro-magnetically coupled {Ru(III)(mu-L(2-))(-)Ru(III)} configuration in 1-6 exhibits complicated overall magnetic and EPR responses,. ne simultaneous presence of highly redox-active quinonoid-bridging ligands and of two ruthenium centers capable of adopting the oxidation states +2, +3, and +4 creates a large variety of possible oxidation state combinations. Accordingly. the complexes 1-6 exhibit two reversible one-electron oxidation steps and at least two reversible reduction processes. Shifts to positive potentials were observed on introduction of Cl substituents (1 -> 2, 3 -> 4) or through replacement of NH by O (6 -> 5). The ligand-to-metal charge transfer (LMCT) absorptions in the visible region of the neutral molecules become more intense and shifted to lower energies on stepwise reduction with two electrons. On oxidation, the para-substituted systems 1-4 exhibit monocation intermediates with intervalence charge transfer (IVCT) transitions of Ru(III)Ru(IV) mixed-valent species. In contrast, the differently substituted systems 5 and 6 show no such near infrared (NIR) absorption. While the first reduction steps are thus assigned to largely ligand-centered processes, the oxidation appears to involve metal-ligand delocalized molecular orbitals with variable degrees of mixing.
 
Publisher WILEY-V C H VERLAG GMBH
 
Date 2011-10-13T18:47:39Z
2011-12-15T09:16:04Z
2011-10-13T18:47:39Z
2011-12-15T09:16:04Z
2008
 
Type Review
 
Identifier CHEMISTRY-A EUROPEAN JOURNAL,14(34)10816-10828
0947-6539
http://dx.doi.org/10.1002/chem.200800976
http://dspace.library.iitb.ac.in/xmlui/handle/10054/13818
http://hdl.handle.net/100/2976
 
Language en