Direct functionalization of the cyclometalated 2-(2′-pyridyl)phenyl ligand bound to iridium(III) |
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| Authors: | Ka-Man Cheung Ka-Wang Chan Ian D Williams |
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| Institution: | a Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, PR China
b Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, PR China |
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| Abstract: | Treatment of Ir(ppy)2(μ-Cl)]2 and Ir(ppy)2(dtbpy)]OTf] (ppy = 2-(2′-pyridyl)phenyl; dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridine; OTf = triflate) with pyridinium tribromide in the presence of Fe powder led to isolation of Ir(4-Br-ppy)(μ-Br)]2 (1) and Ir(4-Br-ppy)2(dtbpy)]OTf] (2), respectively. Pd-catalyzed cross-coupling of 2 with RB(OH)2 afforded Ir(4-R-ppy)2(dtbpy)]OTf] (R = 4′-FC6H4 (3)), 4′-PhC6H4 (4), 2′-thienyl (5), 4′-C6H4CH2OH (6). Treatment of 4 with B2(pin)2 (pin = pinacolate) afforded Ir{4-(pin)B-ppy}2(dtbpy)]OTf] (7). The alkynyl complexes Ir(4-PhC C-ppy)2(dtbpy)]OTf] (8) and Ir{4-Me2(OH)CC-ppy}(4-Br-ppy)(dtbpy)]OTf] (9) were prepared by cross-coupling of 2 with PhCCSnMe3 and Me2C(OH)CCH, respectively. Ethynylation of Ir(fppy)2(dtbpy)]OTf] (fppy = 5-formyl-2-(2′-pyridyl)phenyl) with Ohira’s reagent MeCOC(N2)P(O)(OEt)2 afforded Ir{5-HCC-ppy}2(dtbpy)]OTf] (10). The solid-state structures of 2, 5, 7, and 10 have been determined. |
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| Keywords: | Iridium(III) Cyclometalated ligand Functionalization Cross-coupling |
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