Dani's Paper Online!
"Macrocyclic Triruthenium Complexes Having Electronically Coupled Mixed-Valent States"
Daniel Fink, Michael Bodensteiner, Michael Linseis and Rainer F. Winter
Chemistry – A European Journal, 2018, 24, 4, 992-996
5-Ethynyl-2-furancarboxylic acid or 3-ethynylbenzoic acid self-assemble with HRu(CO)Cl(PiPr3)2 to macrocyclic C3-symmetric triangular triruthenium alkenyl complexes {Ru(CO)(PiPr3)2(CH=CH-Ar-COO)}3 (Ar = C6H4: 1-B, Ar = C4H2O: 1-F). The latter have been characterized by multinuclear NMR spectroscopy, high-resolution ESI-MS mass spectrometry and, in the case of 1-B, by X-ray crystallography. Electrochemical studies indicate that the macrocycles are oxidized in three consecutive one-electron steps. The mixed-valent states obtained by electrochemical or chemical oxidation show signs of valence-delocalization, rendering these complexes rare examples of molecule-based conductive loops with through-bond charge delocalization.
https://dx.doi.org/10.1002/chem.201705143