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dc.contributor.author Yu, Xin
dc.contributor.author Roemmele, Tracey L.
dc.contributor.author Boeré, René T.
dc.date.accessioned 2019-04-24T21:31:24Z
dc.date.available 2019-04-24T21:31:24Z
dc.date.issued 2018
dc.identifier.citation Yu, X., Roemmele, T. L., & Boeré, R. T. (2018). Synthesis, electronic structures, and electrochemistry of 3-triarylphosphoraniminato-1,3,5-trithia-2,4,6,8-tetrazocines: Detection of trithiatetrazocinyl radical anions. ChemElectroChem, 5(6), 968-978. http://dx.doi.org/10.1002/celc.201701191 en_US
dc.identifier.uri https://hdl.handle.net/10133/5340
dc.description Sherpa Romeo green journal. This is the peer reviewed version. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. en_US
dc.description.abstract Reaction of the bicyclic sulfur-nitrogen heterocycles RC6H4CN5S3 (R = 4-CH3O, 4-CH3, 4-H, 4-Cl, 4-CF3, 3-CF3, with PR’3 (R’ =C6H5 or 4-CH3OC6H4) produces 3-phosphoraniminato-7-aryl-1,3,5-trithia-2,4,6,8-tetrazocines RC6H4CN4S3NPR’3. In all cases, only the endo-isomers were isolated and characterized by 1H, 31P, and 19F NMR, UV spectroscopy, and X-ray crystallography. RB3LYP/6-311+G(d,p)// RB3LYP/6-31G(d,p) computations were undertaken to help explain the atom-exact syntheses via intermediates previously detected spectroscopically. Three reasonable intermediates have been computed as stationary points with energies consistent with the observed reaction path. Cyclic and square wave voltammetry studies of RC6H4CN4S3NPR’3 using a glassy carbon working electrode in CH2Cl2 with 0.4 M [nBu4N][PF6] all displayed two IRR reduction processes at RT at approximately –1.9 V and –2.2 V, respectively, and one IRR oxidation process at approximately 1.0 V (versus Fc+/0). [RC6H4CN4S3NPR’3]–• radical anions (R’ = 4-CH3OC6H4, R = 4- CH3O, 4-H, 4-CF3,) were detected at -50 °C in CH2Cl2 by in-situ electrolysis and simultaneous electron paramagnetic resonance spectroscopy: [4-RC6H4CN4S3NP(4-CH3OC6H4)3]–•, estimated a(31P) = 0.078 mT, a(14N1) = 0.031 mT, a(14N2,3) = 0.256 mT, a(14N4,5) = 0.341 mT. The signals decay rapidly but after electrolysis is ended, a persistent EPR signal is always obtained with EPR parameters that match for known 4-aryl-1,2,3,5-dithiadiazolyls, e.g. a(N) = 0.51 mT and g = 2.0105, consistent with production of [4-CF3-C6H4CN2S2]•. en_US
dc.language.iso en_US en_US
dc.publisher Wiley en_US
dc.subject Thiazyl en_US
dc.subject Electrochemistry en_US
dc.subject Redox active en_US
dc.subject Ring compounds en_US
dc.subject Crystallography en_US
dc.subject Electron paramagnetic resonance spectroscopy en_US
dc.subject Reaction pathways en_US
dc.subject Density functional theory en_US
dc.title Synthesis, electronic structures and electrochemistry of 3-triarylphosphoraniminato-1,3,5-trithia-2,4,6,8-tetrazocines: detection of trithiatetrazocinyl radical anions 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
dc.publisher.url https://doi.org/10.1002/celc.201701191


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