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Electronic structure and catalytic aspects of [(trpy)(Cl)Ru(L)](n) incorporating potential non-innocent ligands, L-: 9-Oxidophenalenone and trpy: 2,2 ':6 ',2 ''-terpyridine

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Title Electronic structure and catalytic aspects of [(trpy)(Cl)Ru(L)](n) incorporating potential non-innocent ligands, L-: 9-Oxidophenalenone and trpy: 2,2 ':6 ',2 ''-terpyridine
 
Creator DAS, A
GHOSH, TK
CHOWDHURY, AD
MOBIN, SM
LAHIRI, GK
 
Subject Ruthenium
9-Oxidophenalenone ligand
Structure
Spectro-electrochemistry
Catalysis
BETA-DIKETONATE COMPLEXES
CARBON BOND-CLEAVAGE
WATER-OXIDATION
HYDROGEN-PEROXIDE
BRIDGING LIGAND
ASYMMETRIC EPOXIDATION
DIRUTHENIUM COMPLEX
ALKENE EPOXIDATION
CRYSTAL-STRUCTURE
ORGANIC-COMPOUNDS
 
Description The title complex [(trpy)(Cl)Ru-II(L)] (1) incorporating potential redox non-innocent ligands, L- = 9-oxidophenalenone and trpy = 2,2':6',2 ''-terpyridine has been structurally characterized. The crystal structure of 1 establishes the distorted octahedral arrangement, meridional coordinating mode of trpy and delocalized C-O bond distances of coordinated L-. Compound 1 displays two one-electron oxidations at E-298(0), 0.12 V (Ox1) and 1.32 V (Ox2) and one reduction, -1.58 V versus SCE. Predominantly ruthenium based first oxidation (Ox1) and L based second oxidation (Ox2) lead to the valence configurations of [(trpy)(Cl)Ru-III(L-)](+) (1(+)) and [(trpy)(Cl)Ru-III(L-center dot)](2+) (1(2+)), respectively. The antiferromagnetic coupling of spins on Ru(III) (low-spin, t(2g)(5)) and L-center dot develops a singlet (S = 0) ground state in 1(2+). The reduction, however, occurs at the trpy site. The electronic transitions in 1 and 1(+) could be assigned based on the TD-DFT calculations. Interestingly, 1 has been established to be an efficient pre-catalyst for the oxidative cleavage of alkenes to carbonyl derivatives. (C) 2012 Elsevier Ltd. All rights reserved.
 
Publisher PERGAMON-ELSEVIER SCIENCE LTD
 
Date 2014-10-16T15:07:00Z
2014-10-16T15:07:00Z
2013
 
Type Article
 
Identifier POLYHEDRON, 521130-1137
http://dx.doi.org/10.1016/j.poly.2012.06.057
http://dspace.library.iitb.ac.in/jspui/handle/100/15861
 
Language en