Divinylphenylene bridged diruthenium complexes E,E-[{(PiPr3)2(CO)ClRu}2(µ-HC=CH-C6H4-CH=CH-1,3)] (m-2) and E,E-[{(PiPr3)2(CO)ClRu}2(µ-HC=CH-C6H4-CH=CH-1,4)] (p-
2) have been prepared and compared to their PPh3 containing analogues m-1 and p-1. The higher electron density at the metal atoms increases the contribution of the metal end groups to the bridge-dominated occupied frontier orbitals and stabilizes the various oxidized forms with respect to those of m-1 and p-1. This has been confirmed and quantified electrochemically because the two reversible oxidation waves were observed at considerably lower potentials than for the PPh3 complexes. Owing to their greater stability, the one- and two-electron oxidized forms m-2n+ and p-2n+ of both complexes could be generated and spectroscopically characterized inside an optically transparent thin layer electrolysis cell. UV/Vis/NIR and ESR spectroelectrochemistry indicate that the oxidation processes are centered at the organic bridging ligand. σ-Bonded divinylphenylenes thus constitute an unusual class of ”non-innocent” ligands for organometallic compounds. Electronic transitions observed for the mono- and dioxidized forms closely resemble those of donor-substituted phenylenevinylene compounds including oligophenylenevinylenes (OPVs) and polyphenylenevinylene (PPV) in the respective oxidation states. Strong ESR signals and nearly isotropic g-tensors are observed for the monocations in fluid and frozen solutions. Metal contribution to the redox orbitals is illustrated by a shift of the CO stretching bands to notably higher energies upon stepwise oxidation. The shifts strongly exceed those observed for PPh3 containing six-coordinated species E,E-[{(PPh3)2(CO)Cl(L)Ru}2(µ-HC=CH-C6H4-CH=CH]n+ (L = substituted pyridine). IR spectroelectrochemistry reveals the presence of two electronically different transition metal moieties in m-2+ while they resemble each other more closely in p-2+. Differences in electronic coupling are illustrated by the charge distribution parameters calculated from the spectra. Bulk electrolysis experiments confirm the results from the in situ spectroelectrochemistry and the overall stoichiometry of the redox processes. Quantum chemical calculations were performed in order to provide insight into the nature and composition of the frontier orbitals. The electronic transitions observed for the neutral forms were assigned by TD DFT. IR frequencies calculated for m-2 and p-2 in their various oxidation states retrace the experimental observations. They fail, however, in the case of m-2+, where a symmetrical structure is calculated as opposed to the distinctly asymmetric electron distribution observed by IR spectroscopy. Geometry optimized structures were calculated for all accessible oxidation states. The structural changes following stepwise oxidation agree well with the experimental findings, e. g. a successive low-energy shift of the C=C stretching vibration energy of the bridge. The radical cation m-2+ displays a broad composite electronic absorption band at low energy that extends into the mid-IR region.