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oai:riubu.ubu.es:10259/74072026-02-06T12:52:47Zcom_10259_3592com_10259_3591com_10259.4_106com_10259_2604com_10259_4363com_10259_5086com_10259_6185com_10259_3924col_10259_3930col_10259_4364col_10259_6186col_10259_3925

Echevarría Poza, Igor 833 500 0000-0002-5369-7441 Vaquero Gutiérrez, Mónica 569 600 0000-0002-4550-4072 Manzano, Blanca R. 0f83ceaf-9369-470a-a22b-9b5894978fc0 600 Jalón Sotés, Félix Ángel 83a58ec8-3904-4c18-838c-bcdaf7357757 600 Quesada Pato, Roberto 458 600 0000-0003-2764-7157 Espino Ordóñez, Gustavo 162 600 0000-0001-5617-5705 2023-02-07T09:18:18Z 2023-02-07T09:18:18Z 2022-04 0020-1669 http://hdl.handle.net/10259/7407 10.1021/acs.inorgchem.2c00358 1520-510X Photoredox catalysis constitutes a very powerful tool in organic synthesis, due to its versatility, efficiency, and the mild conditions required by photoinduced transformations. In this paper, we present an efficient and selective photocatalytic procedure for the aerobic oxidative dehydrogenation of partially saturated N-heterocycles to afford the respective N-heteroarenes (indoles, quinolines, acridines, and quinoxalines). The protocol involves the use of new Ir(III) biscyclometalated photocatalysts of the general formula [Ir(C^N)2(N^N′)]Cl, where the C^N ligand is 2- (2,4-difluorophenyl)pyridinate, and N^N′ are different ligands based on the 2-(2′-pyridyl)benzimidazole scaffold. In-depth electrochemical and photophysical studies as well as DFT calculations have allowed us to establish structure−activity relationships, which provide insights for the rational design of efficient metal-based dyes in photocatalytic oxidation reactions. In addition, we have formulated a dual mechanism, mediated by the radical anion superoxide, for the above-mentioned transformations. We acknowledge the financial support provided by the Spanish Ministerio de Ciencia, Innovación y Universidades (RTI2018- 100709-B-C21 and CTQ (QMC)-RED2018-102471-T), Consejería de Educación de la Junta de Castilla y León and FEDER (BU087G19 and BU067P20), and Junta de Comunidades de Castilla-La Mancha-FEDER (JCCM) (grant SBPLY/19/ 180501/000260). I.E. acknowledges his fellowship to both the European Social Fund and Consejería de Educación de la Junta de Castilla y León (EDU/1100/2017). We are also indebted to J. Delgado, P. Castroviejo, and M. Mansilla (PCT of the Universidad de Burgos) for technical support, G. GarcíaHerbosa for providing us access to CV equipment, and J. V. Cuevas-Vicario for support with Gaussian. application/pdf eng American Chemical Society Inorganic Chemistry. 2022, V. 61, n. 16, p. 6193-6208 https://doi.org/10.1021/acs.inorgchem.2c00358 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-100709-B-C21/ES/NUEVOS METALOFARMACOS DISEÑADOS PARA INCREMENTAR LA SELECTIVIDAD EN TRATAMIENTOS CONTRA EL CANCER. USO DE FOTOTERAPIA Y VEHICULIZACION CON LIGANDOS DIRIGIDOS A TUMORES/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RED2018-102471-T/ES/METALOFARMACOS MULTIFUNCIONALES PARA DIAGNOSIS Y TERAPIA/ info:eu-repo/grantAgreement/Junta de Castilla y León//BU087G19//Compuestos organometálicos de ir(iii) en terapias antiproliferativas y como sondas químicas deaminas biógenas/ info:eu-repo/grantAgreement/Junta de Castilla y León//BU067P20//Molecular tools targeting cellular metabolism for cancer therapy/ info:eu-repo/grantAgreement/JCCM//SBPLY%2F19%2F 180501%2F000260/ Atribución 4.0 Internacional http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess Excited states Ligands Redox reactions Solvents Transition metals Química inorgánica Química orgánica Chemistry, Inorganic Chemistry, Organic Photocatalytic Aerobic Dehydrogenation of N-Heterocycles with Ir(III) Photosensitizers Bearing the 2(2′-Pyridyl)benzimidazole Scaffold info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Inorganic Chemistry 61 16 6193 6208 THUMBNAIL Echevarria-ic_2022.pdf.jpg Echevarria-ic_2022.pdf.jpg IM Thumbnail image/jpeg 5318 https://riubu.ubu.es/bitstream/10259/7407/4/Echevarria-ic_2022.pdf.jpg 05d6bca11edcccb673708f2648b9ee2b MD5 4 LICENSE license.txt license.txt text/plain; charset=utf-8 999 https://riubu.ubu.es/bitstream/10259/7407/3/license.txt b295bcbce42e2caabeb0c623d3860c06 MD5 3 CC-LICENSE license_rdf license_rdf application/rdf+xml; charset=utf-8 908 https://riubu.ubu.es/bitstream/10259/7407/2/license_rdf 0175ea4a2d4caec4bbcc37e300941108 MD5 2 ORIGINAL Echevarria-ic_2022.pdf Echevarria-ic_2022.pdf application/pdf 3859059 https://riubu.ubu.es/bitstream/10259/7407/1/Echevarria-ic_2022.pdf 488b33ec9687804746ea85be2ef633e3 MD5 1 10259/7407 oai:riubu.ubu.es:10259/7407 2026-02-06 13:52:47.013 Repositorio Institucional de la Universidad de Burgos bubrep@ubu.es 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