Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes
A diverse set of 2 e−/2 H+ reactions are described that interconvert [RuII(bpy)(en*)2]2+ and [RuIV(bpy)(en‐H*)2]2+ (bpy=2,2′‐bipyridine, en*=H2NCMe2CMe2NH2, en*‐H=H2NCMe2CMe2NH−), forming or cleaving different O−H, N−H, S−H, and C−H bonds. The reactions involve quinones, hydrazines, thiols, and 1,3‐...
| Autores: | , , |
|---|---|
| Formato: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2017 |
| País: | Argentina |
| Recursos: | Consejo Nacional de Investigaciones Científicas y Técnicas |
| Repositorio: | CONICET Digital (CONICET) |
| Idioma: | inglés |
| OAI Identifier: | oai:ri.conicet.gov.ar:11336/43385 |
| Acesso em linha: | http://hdl.handle.net/11336/43385 |
| Access Level: | acceso abierto |
| Palavra-chave: | Multiredox Proton-Coupled Electron Transfer (Pcet) Ruthenium Amido Multielectron Multiproton https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
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Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido ComplexesCattaneo, MauricioRyken, Scott A.Mayer, James M.MultiredoxProton-Coupled Electron Transfer (Pcet)RutheniumAmidoMultielectronMultiprotonhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A diverse set of 2 e−/2 H+ reactions are described that interconvert [RuII(bpy)(en*)2]2+ and [RuIV(bpy)(en‐H*)2]2+ (bpy=2,2′‐bipyridine, en*=H2NCMe2CMe2NH2, en*‐H=H2NCMe2CMe2NH−), forming or cleaving different O−H, N−H, S−H, and C−H bonds. The reactions involve quinones, hydrazines, thiols, and 1,3‐cyclohexadiene. These proton‐coupled electron transfer reactions occur without substrate binding to the ruthenium center, but instead with precursor complex formation by hydrogen bonding. The free energies of the reactions vary over more than 90 kcal mol−1, but the rates are more dependent on the type of X−H bond involved than the associated ΔG°. There is a kinetic preference for substrates that have the transferring hydrogen atoms in close proximity, such as ortho‐tetrachlorobenzoquinone over its para‐isomer and 1,3‐cyclohexadiene over its 1,4‐isomer, perhaps hinting at the potential for concerted 2 e−/2 H+ transfers.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. University of Washington; Estados UnidosFil: Ryken, Scott A.. University of Washington; Estados UnidosFil: Mayer, James M.. University of Yale; Estados Unidos. University of Washington; Estados UnidosWiley VCH Verlag2017-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/43385Cattaneo, Mauricio; Ryken, Scott A.; Mayer, James M.; Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes; Wiley VCH Verlag; Angewandte Chemie; 56; 13; 3-2017; 3675-36781433-7851CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201612642info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.201612642info:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5812014/info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2024-05-08T13:32:55Zoai:ri.conicet.gov.ar:11336/43385instacron: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:34982024-05-08 13:32:55.467CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse |
| dc.title.none.fl_str_mv |
Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes |
| title |
Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes |
| spellingShingle |
Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes Cattaneo, Mauricio Multiredox Proton-Coupled Electron Transfer (Pcet) Ruthenium Amido Multielectron Multiproton https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| title_short |
Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes |
| title_full |
Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes |
| title_fullStr |
Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes |
| title_full_unstemmed |
Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes |
| title_sort |
Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes |
| dc.creator.none.fl_str_mv |
Cattaneo, Mauricio Ryken, Scott A. Mayer, James M. |
| author |
Cattaneo, Mauricio |
| author_facet |
Cattaneo, Mauricio Ryken, Scott A. Mayer, James M. |
| author_role |
author |
| author2 |
Ryken, Scott A. Mayer, James M. |
| author2_role |
author author |
| dc.subject.none.fl_str_mv |
Multiredox Proton-Coupled Electron Transfer (Pcet) Ruthenium Amido Multielectron Multiproton https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| topic |
Multiredox Proton-Coupled Electron Transfer (Pcet) Ruthenium Amido Multielectron Multiproton https://purl.org/becyt/ford/1.4 https://purl.org/becyt/ford/1 |
| description |
A diverse set of 2 e−/2 H+ reactions are described that interconvert [RuII(bpy)(en*)2]2+ and [RuIV(bpy)(en‐H*)2]2+ (bpy=2,2′‐bipyridine, en*=H2NCMe2CMe2NH2, en*‐H=H2NCMe2CMe2NH−), forming or cleaving different O−H, N−H, S−H, and C−H bonds. The reactions involve quinones, hydrazines, thiols, and 1,3‐cyclohexadiene. These proton‐coupled electron transfer reactions occur without substrate binding to the ruthenium center, but instead with precursor complex formation by hydrogen bonding. The free energies of the reactions vary over more than 90 kcal mol−1, but the rates are more dependent on the type of X−H bond involved than the associated ΔG°. There is a kinetic preference for substrates that have the transferring hydrogen atoms in close proximity, such as ortho‐tetrachlorobenzoquinone over its para‐isomer and 1,3‐cyclohexadiene over its 1,4‐isomer, perhaps hinting at the potential for concerted 2 e−/2 H+ transfers. |
| publishDate |
2017 |
| dc.date.none.fl_str_mv |
2017-03 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
| format |
article |
| status_str |
publishedVersion |
| dc.identifier.none.fl_str_mv |
http://hdl.handle.net/11336/43385 Cattaneo, Mauricio; Ryken, Scott A.; Mayer, James M.; Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes; Wiley VCH Verlag; Angewandte Chemie; 56; 13; 3-2017; 3675-3678 1433-7851 CONICET Digital CONICET |
| url |
http://hdl.handle.net/11336/43385 |
| identifier_str_mv |
Cattaneo, Mauricio; Ryken, Scott A.; Mayer, James M.; Outer-Sphere 2 e − /2 H + Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes; Wiley VCH Verlag; Angewandte Chemie; 56; 13; 3-2017; 3675-3678 1433-7851 CONICET Digital CONICET |
| dc.language.none.fl_str_mv |
eng |
| language |
eng |
| dc.relation.none.fl_str_mv |
info:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201612642 info:eu-repo/semantics/altIdentifier/doi/10.1002/anie.201612642 info:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5812014/ |
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info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
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openAccess |
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https://creativecommons.org/licenses/by-nc-sa/2.5/ar/ |
| dc.format.none.fl_str_mv |
application/pdf application/pdf application/pdf |
| dc.publisher.none.fl_str_mv |
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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Consejo Nacional de Investigaciones Científicas y Técnicas |
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CONICET Digital (CONICET) |
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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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