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Theoretical Perspectives on Redox "Non-Innocent" Oxazolidine N-Oxide Iron Nitroxide Complexes

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Title Theoretical Perspectives on Redox "Non-Innocent" Oxazolidine N-Oxide Iron Nitroxide Complexes
 
Creator TEWARY, S
GASS, IA
MURRAY, KS
RAJARAMAN, G
 
Subject Radicals
Iron
Density functional calculations
Spin crossover
Magnetic properties
DENSITY-FUNCTIONAL THEORY
EXCHANGE COUPLING-CONSTANTS
TRANSITION-METAL-COMPLEXES
GAUSSIAN-BASIS SETS
ORGANIC FERROMAGNET
MAGNETIC-PROPERTIES
CORRELATION-ENERGY
SPIN-CROSSOVER
HYBRID FUNCTIONALS
HARTREE-FOCK
 
Description One-electron redox processes in ligands that exhibit non-innocent behaviour invariably leads to the generation of radical species, which, when coupled with redox-active metal centres, can lead to strong magnetic exchange, ambiguous electronic structures and even spin crossover (SCO). We have chosen two iron complexes [Fe-II(L-center dot)(2)](BF4)(2) (1) and [Fe-III(L-)(2)](BPh4) (2) [with L-center dot = 4-dimethyl-2,2-di(2-pyridyl)oxazolidine N-oxide] as the basis for an extensive theoretical study to determine the influence and interplay of the strong magnetic exchange, the redox non-innocent behaviour and any possible spin transitions. A series of calculations established the low-spin character of the Fe in both the complexes and gave us valuable insight into the electronic structure of 1 and 2 along with their one- and two-electron reduced species. An attempt has been made to relate the bonding features to the energy difference between different spin states and to the influence of the exchange coupling on any possible SCO properties.
 
Publisher WILEY-V C H VERLAG GMBH
 
Date 2014-10-14T17:08:19Z
2014-10-14T17:08:19Z
2013
 
Type Article
 
Identifier EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (5-6)1024-1032
http://dx.doi.org/10.1002/ejic.201201077
http://dspace.library.iitb.ac.in/jspui/handle/100/14529
 
Language en