2-Mercaptobenzoxazole pentacyanoferrate(II/III) complexes: UV-Visible, Mössbauer, electron paramagnetic resonance, electrochemistry and molecular modeling

Journal of the Brazilian Chemical Society

Juciane B Luiz²  Fabiano M. De Andrade²  Eduardo L. De Sá²  Geraldo R Friedermann²  Antonio S Mangrich²  J. Elaine Barclay¹  David J Evans¹  Tai Hasegawa¹  Fábio S Nunes² 

[1] ,Universidade Federal do Paraná Centro Politécnico Departamento de QuímicaCuritiba PR ,Brazil

关键词: 2-mercaptobenzoxazole;    pentacyanoferrate;    spectroscopy;    crystal field parameters;    ab initio calculations;    electrochemistry;   

DOI  :  10.1590/S0103-50532004000100003

来源: SciELO

【 摘 要 】

2-Mercaptobenzoxazole pentacyanoferrate(II/III) complexes, [FeII/III(CN)5(bzoxs)]3-/2- , were prepared in MeOH/H2O 75:25% solutions and characterized by spectroscopic UV-Vis, Mössbauer, electron paramagnetic resonance (epr) and electrochemical-cyclic voltammetry- techniques. UV-Vis and epr spectra along with the electrochemical behavior suggested the coordination of the multi-functional N,S,O- donor ligand, bzoxs, to iron(III) through the sulfur atom. The crystal field parameters, DqL and Dt, calculated for the iron(II) complex, in addition to the reversible redox process FeIII-bzoxs + e- -> FeII-bzoxs also pointed to coordination via the sulfur atom. The results were compared with the chemical properties of pentacyanoferrate complexes containing other monodentate N-, S- and O-donor ligands. Ab initio calculations revealed the composition of the frontier orbitals of bzoxs and are in agreement with the mode of coordination proposed from the experimental data.

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