Abstract
We report on a series of dinuclear 1,4-divinylanthrylene-bridged diruthenium complexes 1A-Ru-PR3 with different phosphine ligands (PiPr3, PiPr2Me, PPh3, and PMe3) and with coordination numbers of five or six. All compounds were characterized by NMR spectroscopy, high resolution ESI-MS and, in the case of 1A-Ru-PiPr3 and 1A-Ru-PMe3, single crystal X-ray diffraction. Cyclic voltammetry measurements reveal that the PR3 ligands, besides tuning the redox potentials, exert a strong influence on the stability of their one- and two-electron oxidized forms. Information on the charge- and spin-density distribution was obtained by IR, UV/Vis/NIR and EPR spectroscopy. Our results indicate full charge and spin delocalization in 1A-Ru-PiPr3•+, 1A-Ru-PMe3•+ and macrocyclic, isophthalate-bridged 2A-Ru-PiPr2Me••2+, whereas 1A-Ru-PiPr2Me•+ constitutes a peculiar case, where valence-delocalized and valence-localized structures seem to coexist.
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