RT info:eu-repo/semantics/article T1 η6-Hexahelicene Complexes of Iridium and Ruthenium: Running along the Helix A1 Álvarez González, Celedonio Manuel A1 Barbero San Juan, Héctor A1 García-Escudero, Luis A. A1 Martín Álvarez, José Miguel A1 Martínez-Pérez, Cristina A1 Miguel San José, Daniel AB The first η6-complexes of iridium and ruthenium coordinated to helicenes have been obtained. Hexahelicene (1), 2,15-dimethylhexahelicene (2), and 2,15-dibromohexahelicene (3) react with [Cp*IrCl2]2 and AgBF4 in CD3NO2 to afford quantitatively the complexes [Cp*Ir(η6-1)][BF4]2 (4A), [Cp*Ir(η6-2)][BF4]2 (5A), and [Cp*Ir(η6-3)][BF4]2 (6A), respectively. In all cases, the final thermodynamic products are similar, and they exhibit coordination between the 12 e– metal fragment [IrCp*]2+ and the terminal ring of the helicene. Monitoring the reaction by NMR shows formation of intermediates, some of which have been fully characterized in solution. These intermediates exhibit the metal fragment coordinated to the internal rings. We have also synthesized the bimetallic complex [(Cp*Ir)2(μ2-η6:η6-2)][BF4]4 (7), achieving coordination between two units [IrCp*]2+ and the helicene 2. Following an analogous methodology, we have prepared the complex [(η6-cymene)Ru(η6-2)][BF4]2 (8), which has been studied by X-ray diffraction, confirming the preferential binding to the terminal aromatic ring. PB American Chemical Society SN 0020-1669 YR 2012 FD 2012 LK https://uvadoc.uva.es/handle/10324/65797 UL https://uvadoc.uva.es/handle/10324/65797 LA eng NO Inorg. Chem. 2012, 51, 15, 8103–8111 NO Producción Científica DS UVaDOC RD 17-jul-2024