Synthesis, electronic structures and electrochemistry of 3-triarylphosphoraniminato-1,3,5-trithia-2,4,6,8-tetrazocines: detection of trithiatetrazocinyl radical anions

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dc.contributor.authorYu, Xin
dc.contributor.authorRoemmele, Tracey L.
dc.contributor.authorBoeré, René T.
dc.date.accessioned2019-04-24T21:31:24Z
dc.date.available2019-04-24T21:31:24Z
dc.date.issued2018
dc.descriptionAccepted peer reviewed author manuscript. 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.abstractReaction 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.description.peer-reviewYesen_US
dc.identifier.citationYu, 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.201701191en_US
dc.identifier.urihttps://hdl.handle.net/10133/5340
dc.language.isoen_USen_US
dc.publisherWileyen_US
dc.publisher.departmentDepartment of Chemistry and Biochemistryen_US
dc.publisher.facultyArts and Scienceen_US
dc.publisher.institutionUniversity of Lethbridgeen_US
dc.publisher.urlhttps://doi.org/10.1002/celc.201701191
dc.subjectThiazylen_US
dc.subjectElectrochemistryen_US
dc.subjectRedox activeen_US
dc.subjectRing compoundsen_US
dc.subjectCrystallographyen_US
dc.subjectElectron paramagnetic resonance spectroscopyen_US
dc.subjectReaction pathwaysen_US
dc.subjectDensity functional theoryen_US
dc.titleSynthesis, electronic structures and electrochemistry of 3-triarylphosphoraniminato-1,3,5-trithia-2,4,6,8-tetrazocines: detection of trithiatetrazocinyl radical anionsen_US
dc.typeArticleen_US
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