Artículo
2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton Transfer
Cattaneo, Mauricio
; Schiewer, Christine; Schober, Anne; Dechert, Sebastian; Siewert, Inke; Meyer, Franc
Fecha de publicación:
01/2018
Editorial:
Wiley VCH Verlag
Revista:
Chemistry- A European Journal
ISSN:
0947-6539
Idioma:
Inglés
Tipo de recurso:
Artículo publicado
Clasificación temática:
Resumen
[1,2]dithiino[4,3-b:5,6-b´]dipyridine (1) and its protonated open form 3,3´-dithiol-2,2´-bipyridine (2) were synthesised and their interconversion investigated. The X-ray structure of 2 revealed an anti orientation of the two pyridine units and a zwitterionic form. In depth electrochemical studies in combination with DFT calculations lead to a comprehensive picture of the redox chemistry of 1 in the absence and presence of protons. Initial one electron reduction at E1 = −1.97 V results in the formation of the radical anion 1red with much elongated S-S bond, which readily undergoes further reduction at E2 = −2.15 V. Water triggers a potential inversion (E ≥ −1.9 V for the second reduction) as the radical anion 1red is protonated at its basic N atom. DFT studies revealed that S−S bond breaking and twisting of the pyridine units generally occurs after the second reduction step while the potential inversion induced by protonation is a result of charge compensation. The CV data were simulated to derive rate constants for the individual chemical and electrochemical reactions for both scenarios in the absence and presence of protons.
Palabras clave:
disulfide
,
bipyridine ligands
,
multiredox
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Colecciones
Articulos(INQUINOA)
Articulos de INST.DE QUIMICA DEL NOROESTE
Articulos de INST.DE QUIMICA DEL NOROESTE
Citación
Cattaneo, Mauricio; Schiewer, Christine; Schober, Anne; Dechert, Sebastian; Siewert, Inke; et al.; 2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton Transfer; Wiley VCH Verlag; Chemistry- A European Journal; 1-2018
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