134840 20260217205450.0 doi 10.1021/acs.inorgchem.4c00115 sideral 138347 ART-2024-138347 eng Benítez, María C–H, N–H, and O–H Bond Activations to Prepare Phosphorescent Hydride-Iridium(III)-Phosphine Emitters with Photocatalytic Achievement in C–C Coupling Reactions 2024 Complex IrH5(PiPr3)2 (1) activates two different σ-bonds of 3-phenoxy-1-phenylisoquinoline, 2-(1H-benzimidazol-2-yl)-6-phenylpyridine, 2-(1H-indol-2-yl)-6-phenylpyridine, 2-(2-hydroxyphenyl)-6-phenylpyridine, N-(2-hydroxyphenyl)-N′-phenylimidazolylidene, and 1,3-di(2-pyridyl)-4,6-dimethylbenzene to give IrH{κ3-C,N,C-[C6H4-isoqui-O-C6H4]}(PiPr3)2 (2), IrH{κ3-N,N,C-[NBzim-py-C6H4]}(PiPr3)2 (3), IrH{κ3-N,N,C-[Ind-py-C6H4]}(PiPr3)2 (4), IrH{κ3-C,N,O-[C6H4-py-C6H4O]}(PiPr3)2 (5), IrH{κ3-C,C,O-[C6H4-Im-C6H4O]}(PiPr3)2 (6), and IrH{κ3-N,C,C-[py-C6HMe2-C5H3N]}(PiPr3)2 (7), respectively. The activations are sequential, with the second generally being the slowest. Accordingly, dihydride intermediates IrH2{κ2-C,N-[C6H4-isoqui-O-C6H5]}(PiPr3)2 (2d), IrH2{κ2-N,N-[NBzim-py-C6H5]}(PiPr3)2 (3d), IrH2{κ2-N,N-[Ind-py-C6H5]}(PiPr3)2 (4d), and IrH2{κ2-N,C-[py-C6HMe2-py]}(PiPr3)2 (7d) were characterized spectroscopically. Complexes 3 and 5 are green phosphorescent emitters upon photoexcitation, exhibiting good absorption over a wide range of wavelengths, emission quantum yields about 0.70 in solution, long enough lifetimes (10–17 μs), and reversible electrochemical behavior. In agreement with these features, complex 3 promotes the photocatalytic α-amino C(sp3)–H arylation of N,N-dimethylaniline and N-phenylpiperidine with 1,4-dicyanobenzene and 4-cyanopyridine under blue LED light irradiation. The C–C coupling products are isolated in high yields with only 2 mol % of photocatalyst after 24 h. info:eu-repo/grantAgreement/ES/DGA/E06-23R info:eu-repo/grantAgreement/ES/MICINN/PID2020-115286GB-I00/AEI/10.13039/501100011033 info:eu-repo/grantAgreement/ES/MICINN/RED2022-134287-T info:eu-repo/semantics/closedAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 4.7 2024 CHEMISTRY, INORGANIC & NUCLEAR 6 / 43 = 0.14 2024 Q1 T1 0.958 2024 Chemistry (miscellaneous) 2024 Q1 Physical and Theoretical Chemistry 2024 Q1 Inorganic Chemistry 2024 Q1 7.4 2024 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Buil, María L. Universidad de Zaragoza (orcid)0000-0002-3284-1053 Esteruelas, Miguel A. (orcid)0000-0002-4829-7590 López, Ana M. Universidad de Zaragoza (orcid)0000-0001-7183-4975 Martín-Escura, Cristina Universidad de Zaragoza Oñate, Enrique (orcid)0000-0003-2094-719X 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 63, 14 (2024), 6346-6361 Inorg. chem. Inorganic Chemistry 0020-1669 2952228 http://zaguan.unizar.es/record/134840/files/texto_completo.pdf Versión publicada 2996419 http://zaguan.unizar.es/record/134840/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:134840 articulos driver 2026-02-17-20:18:57 ARTICLE