2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton Transfer
- Autores
- Cattaneo, Mauricio; Schiewer, Christine; Schober, Anne; Dechert, Sebastian; Siewert, Inke; Meyer, Franc
- Año de publicación
- 2018
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- [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.
Fil: Cattaneo, Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Schiewer, Christine. Universität Göttingen; Alemania
Fil: Schober, Anne. Universität Göttingen; Alemania
Fil: Dechert, Sebastian. Universität Göttingen; Alemania
Fil: Siewert, Inke. Universität Göttingen; Alemania
Fil: Meyer, Franc. Universität Göttingen; Alemania - Materia
-
disulfide
bipyridine ligands
multiredox - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
- Repositorio
.jpg)
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/85505
Ver los metadatos del registro completo
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2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton TransferCattaneo, MauricioSchiewer, ChristineSchober, AnneDechert, SebastianSiewert, InkeMeyer, Francdisulfidebipyridine ligandsmultiredoxhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1[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.Fil: Cattaneo, Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Schiewer, Christine. Universität Göttingen; AlemaniaFil: Schober, Anne. Universität Göttingen; AlemaniaFil: Dechert, Sebastian. Universität Göttingen; AlemaniaFil: Siewert, Inke. Universität Göttingen; AlemaniaFil: Meyer, Franc. Universität Göttingen; AlemaniaWiley VCH Verlag2018-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/85505Cattaneo, 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; 1-20180947-6539CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://doi.wiley.com/10.1002/chem.201705022info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201705022info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:49:27Zoai:ri.conicet.gov.ar:11336/85505instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 09:49:27.593CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
| dc.title.none.fl_str_mv |
2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton Transfer |
| title |
2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton Transfer |
| spellingShingle |
2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton Transfer Cattaneo, Mauricio disulfide bipyridine ligands multiredox |
| title_short |
2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton Transfer |
| title_full |
2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton Transfer |
| title_fullStr |
2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton Transfer |
| title_full_unstemmed |
2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton Transfer |
| title_sort |
2,2'-Bipyridine Equipped with a Disulfide/Dithiol Switch for Coupled Two Electron and Proton Transfer |
| dc.creator.none.fl_str_mv |
Cattaneo, Mauricio Schiewer, Christine Schober, Anne Dechert, Sebastian Siewert, Inke Meyer, Franc |
| author |
Cattaneo, Mauricio |
| author_facet |
Cattaneo, Mauricio Schiewer, Christine Schober, Anne Dechert, Sebastian Siewert, Inke Meyer, Franc |
| author_role |
author |
| author2 |
Schiewer, Christine Schober, Anne Dechert, Sebastian Siewert, Inke Meyer, Franc |
| author2_role |
author author author author author |
| dc.subject.none.fl_str_mv |
disulfide bipyridine ligands multiredox |
| topic |
disulfide bipyridine ligands multiredox |
| purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| dc.description.none.fl_txt_mv |
[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. Fil: Cattaneo, Mauricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina Fil: Schiewer, Christine. Universität Göttingen; Alemania Fil: Schober, Anne. Universität Göttingen; Alemania Fil: Dechert, Sebastian. Universität Göttingen; Alemania Fil: Siewert, Inke. Universität Göttingen; Alemania Fil: Meyer, Franc. Universität Göttingen; Alemania |
| description |
[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. |
| publishDate |
2018 |
| dc.date.none.fl_str_mv |
2018-01 |
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info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
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article |
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publishedVersion |
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http://hdl.handle.net/11336/85505 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 0947-6539 CONICET Digital CONICET |
| url |
http://hdl.handle.net/11336/85505 |
| identifier_str_mv |
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 0947-6539 CONICET Digital CONICET |
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eng |
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eng |
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info:eu-repo/semantics/altIdentifier/url/http://doi.wiley.com/10.1002/chem.201705022 info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201705022 |
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openAccess |
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application/pdf application/pdf |
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Wiley VCH Verlag |
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Wiley VCH Verlag |
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reponame:CONICET Digital (CONICET) instname:Consejo Nacional de Investigaciones Científicas y Técnicas |
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CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas |
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dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar |
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