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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
η6-Hexahelicene complexes of iridium and ruthenium: running along the helix
Celedonio M Álvarez1, Héctor Barbero, Luis A García-Escudero
1IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, E-47005, Valladolid, Spain. celedonio.alvarez@uva.es
Abstract:
The first η(6)-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*IrCl(2)](2) and AgBF(4) in CD(3)NO(2) to afford quantitatively the complexes [Cp*Ir(η(6)-1)][BF(4)](2) (4A), [Cp*Ir(η(6)-2)][BF(4)](2) (5A), and [Cp*Ir(η(6)-3)][BF(4)](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)(μ(2)-η(6):η(6)-2)][BF(4)](4) (7), achieving coordination between two units [IrCp*](2+) and the helicene 2. Following an analogous methodology, we have prepared the complex [(η(6)-cymene)Ru(η(6)-2)][BF(4)](2) (8), which has been studied by X-ray diffraction, confirming the preferential binding to the terminal aromatic ring.
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