Show simple item record Boeré, René T. Roemmele, Tracey L. Yu, Xin 2019-03-29T22:20:12Z 2019-03-29T22:20:12Z 2011
dc.identifier.citation Boeré, R. T., Roemmele, T. L., & Yu, X. (2011). Unsymmetrical (1λ3)-1,2,4,6-thiatriazinyls with aryl and trifluoromethyl substituents: Synthesis, crystal structures, EPR spectroscopy and voltammetry. Inorganic Chemistry, 50(11), 5123-5135. doi: 10.1021/ic2003996 en_US
dc.description Sherpa Romeo white journal. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. en_US
dc.description.abstract A general synthetic route to 3-trifluoromethyl-5-aryl-1λ3-1,2,4,6-thiatriazinyl radicals was developed. X-ray structures were obtained for all five neutral radicals and show that they exist in the solid state as co-facial dimers linked by S···S contacts. X-ray structures were also obtained for two of the precursor chlorothiatriazines along with several aryl N-imidoylamidines, p-methoxybenzamidine and N-chlorosulfonyl-N,N'-benzamidine. Cyclic voltammetric studies were performed on the [R2C2N3S]• radicals in CH3CN and CH2Cl2 with [nBu4N][PF6] as the supporting electrolyte under vacuum in an all-glass electrochemical cell. The results provide quasi-reversible formal potentials for the [R2C2N3S]−/0 process in the range of −0.61 to −0.47 V, irreversible peak potentials for the [R2C2N3S]0/+ process from 0.59 to 0.91 V at lower concentrations, and the appearance of a second, reversible oxidation process from 0.69 to 0.94 V at higher concentrations (versus the Fc0/+ couple; Fc = Ferrocene). This behavior was indicative of monomer-dimer equilibrium in solution as ascertained from digital models of the voltammograms. There is a small but measurable trend in both the oxidation and reduction potentials with varying remote aryl substituents. EPR spectra were obtained for all five neutral radicals in CH2Cl2 solutions, which confirm concentration of the unpaired electron density on the heterocyclic core. Trends were also seen in the hyperfine splitting constants aN with varying remote aryl substituents. Calculations were performed for all three oxidation states of the [R2C2N3S]-/•/+ monomeric rings; the resulting theoretical redox energies correlate well with solution phase voltammetric data. en_US
dc.language.iso en_US en_US
dc.publisher ACS Publications en_US
dc.subject Free radical en_US
dc.subject Thiatriazinyl en_US
dc.subject Electron paramagnetic resonance en_US
dc.subject Cyclic voltammetry en_US
dc.subject Ionization potential en_US
dc.subject Electrochemistry en_US
dc.subject DFT calculations en_US
dc.subject.lcsh Free radicals (Chemistry)
dc.subject.lcsh Voltammetry
dc.subject.lcsh Ionization
dc.subject.lcsh Electron paramagnetic resonance spectroscopy
dc.title Unsymmetrical (1-λ3)-1,2,4,6-thiatriazinyls with aryl and trifluoromethyl substituents: synthesis, crystal structures, EPR spectroscopy and voltammetry en_US
dc.type Article en_US
dc.publisher.faculty Arts and Science en_US
dc.publisher.department Department of Chemistry and Biochemistry en_US
dc.description.peer-review Yes en_US
dc.publisher.institution University of Lethbridge en_US

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