doi:10.1021/acs.inorgchem.4c00115engBenítez, MaríaBuil, María L.Esteruelas, Miguel A.López, Ana M.Martín-Escura, CristinaOñate, EnriqueC–H, N–H, and O–H Bond Activations to Prepare Phosphorescent Hydride-Iridium(III)-Phosphine Emitters with Photocatalytic Achievement in C–C Coupling ReactionsART-2024-138347Complex 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.2024http://zaguan.unizar.es/record/13484010.1021/acs.inorgchem.4c00115http://zaguan.unizar.es/record/134840oai:zaguan.unizar.es:134840info:eu-repo/grantAgreement/ES/DGA/E06-23Rinfo:eu-repo/grantAgreement/ES/MICINN/PID2020-115286GB-I00/AEI/10.13039/501100011033info:eu-repo/grantAgreement/ES/MICINN/RED2022-134287-TInorganic Chemistry 63, 14 (2024), 6346-6361All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/closedAccess