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Cyclic Homo- and Heterohalogen Di-λ3-diarylhalonium Structures Chen, Wei W. Artigues Cladera, Margalida Font-Bardia, Mercè Cuenca, Ana Belen Shafir, Alexandr Universitat Ramon Llull. IQS Aromatic compounds Chemical structure Group 17 compounds Reaction products Salts Compostos aromàtics Estructura química Elements químics Reactivitat (Química) Sals 544 546 547 In the context of the ever-growing interest in the cyclic diaryliodonium salts, this work presents synthetic design principles for a new family of structures with two hypervalent halogens in the ring. The smallest bis-phenylene derivative, [(C6H4)2I2]2+, was prepared through oxidative dimerization of a precursor bearing the ortho-disposed iodine and trifluoroborate groups. We also report, for the first time, the formation of cycles containing two different halogen atoms. These present two phenylenes linked by hetero-(I/Br) or -(I/Cl) halogen pairs. This approach was also extended to the cyclic bis-naphthylene derivative [(C10H6)2I2]2+. The structures of these bis-halogen(III) rings were further assessed through X-ray analysis. The simplest cyclic phenylene bis-iodine(III) derivative features the interplanar angle of ∼120°, while a smaller angle of ∼103° was found for the analogous naphthylene-based salt. All dications form dimeric pairs through a combination of π–π and C–H/π interactions. As the largest member of the family, a bis-I(III)-macrocycle was also assembled using the quasi-planar xanthene backbone. Its geometry enables the two iodine(III) centers to be bridged intramolecularly by two bidentate triflate anions. In a preliminary manner, the interaction of the phenylene- and naphthalene-based bis-iodine(III) dications with a new family of rigid bidentate bis-pyridine ligands was studied in solution and the solid state, with an X-ray structure showing the chelating donor bonding to just one of the two iodine centers. info:eu-repo/semantics/publishedVersion 2023-06-28 info:eu-repo/semantics/article 1520-5126 http://hdl.handle.net/20.500.14342/4646 https://doi.org/10.1021/jacs.3c02406 eng Journal of the American Chemical Society 2023, 145 (25), 13796–13804 info:eu-repo/grantAgreement/MCI/PN I+D/PID2020-113661GB-I00 info:eu-repo/grantAgreement/SUR del DEC/SGR/2021 SGR 00520 info:eu-repo/grantAgreement/SUR del DEC/SGR/2017 SGR 01051 © L'autor/a Attribution 4.0 International http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess p.9 American Chemical Society