Synthesis, electrochemistry and in situ spectroelectrochemistry of a new Co(III) thio Schiff-base complex with N,N?-bis(2-aminothiophenol)-1,4-bis(carboxylidene phenoxy)butane

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dc.contributor.authorYilmaz, Ismail
dc.contributor.authorTemel, Hamdi
dc.contributor.authorAlp, Hueseyin
dc.date.accessioned2024-04-24T16:18:17Z
dc.date.available2024-04-24T16:18:17Z
dc.date.issued2008
dc.departmentDicle Üniversitesien_US
dc.description.abstractA new cobalt Schiff-base complex, [Co(L)(OH)(H2O)] (where L = [N,N'-bis(2-aminothiophenol)-1,4-bis(carboxylidene phenoxy)butane), was synthesized and its electrochemical and spectroelectochemical properties were investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and thin-layer spectro-electrochemistry in solutions of dimethyl sulfoxide (DMSO) and dichloromethane (CH2O2). The [Co(L)(OH)(H2O)] complex displays two well-defined reversible reduction processes with the corresponding anodic waves. The half-wave potentials of the first and second reduction processes were displayed at E-1/2 = 0.08 V and E-1/2 = -1.21 V (scan rate: 0.100 Vs(-1)) in DMSO, and E-1/2 = -0.124 V and E-1/2 = -1.32 V (scan rate: 0.100 Vs(-1)) in CH2Cl2. The potentials of the reduction processes in DMSO are shifted toward negative potentials (0.220-0.112 V) compared to those in CH2O2. The electrochemical results are assigned to two one-electron reduction processes; [Co(III)L] + (-)e -> [Co(II)L](-) and [Co(II)L](-) + (-)e -> [Co(I)L](2-). The six-coordination of the complex remains unchanged during the reduction processes and the electron transfer processes were not followed by a chemical reaction upon scan reversal. It was also seen that [Co(L)(OH)(H2O)1 was reduced at a more positive potential than the corresponding salen analogs. The shift and reversibility are apparently related to the high degree of electron delocalization of the [Co(L)(OH)(H2O)] complex, having a N2O2S2 donor set and two additional benzene units. Additionally, in situ spectro-electrochemical measurements support Co(III)/Co(II) and Co(II)/Co(I) reversible reduction processes with the observation of the corresponding spectral changes with the applied potentials E-app = -0.40 and -1.60 V. Application of the spectroelectrochernical results allowed the determination of E-1/2 and n (the number of electrons) from the spectra of the fully oxidized and reduced species in one unified experiment as well. The results obtained by this method are in agreement with those by the CV and DPV methods. (C) 2007 Elsevier Ltd. All rights reserved.en_US
dc.identifier.doi10.1016/j.poly.2007.08.044
dc.identifier.endpage132en_US
dc.identifier.issn0277-5387
dc.identifier.issue1en_US
dc.identifier.scopus2-s2.0-37349054402
dc.identifier.scopusqualityQ2
dc.identifier.startpage125en_US
dc.identifier.urihttps://doi.org/10.1016/j.poly.2007.08.044
dc.identifier.urihttps://hdl.handle.net/11468/15954
dc.identifier.volume27en_US
dc.identifier.wosWOS:000253191100016
dc.identifier.wosqualityQ2
dc.indekslendigikaynakWeb of Science
dc.indekslendigikaynakScopus
dc.language.isoenen_US
dc.publisherPergamon-Elsevier Science Ltden_US
dc.relation.ispartofPolyhedron
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subjectSchiff-Baseen_US
dc.subjectThiosalenen_US
dc.subjectCobalten_US
dc.subjectElectrochemistryen_US
dc.subjectSpectroelectrochemistryen_US
dc.titleSynthesis, electrochemistry and in situ spectroelectrochemistry of a new Co(III) thio Schiff-base complex with N,N?-bis(2-aminothiophenol)-1,4-bis(carboxylidene phenoxy)butaneen_US
dc.titleSynthesis, electrochemistry and in situ spectroelectrochemistry of a new Co(III) thio Schiff-base complex with N,N?-bis(2-aminothiophenol)-1,4-bis(carboxylidene phenoxy)butane
dc.typeArticleen_US

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