From paddlewheel starting reactants Ru(R'CO), a family of edge-sharing bi-octahedral (ESBO) diruthenium(III,III) compounds has been prepared, formulated as Ru(μ-OCR')(μ-OR)(η-L) (1-10) [R' = CH, R = CH, L = acac (1), tfac (2); R' = CH, R = CHCH, L = hfac (3); R' = CHCH, R = CH, L = acac (4), tfac (5); R' = CHCH, R = CHCH, L = hfac (6); R' = CHCl, R = CH, L = tfac (7); R' = CHCl, R = CHCH, L = hfac (8); R' = CH, R = CH, L = tfac (9); and R' = H, R = CH, L = acac (10); here, acac, tfac and hfac represent acetylacetone, trifluoroacetylacetone and hexafluoroacetylacetone, respectively]. Compounds 1-10 have a similar ESBO coordination geometry of the Ru(μ-OCR')(μ-OR)Ru core with a Ru-Ru center chelated and bridged by two μ-OCR' and two μ-OR in a manner, and each Ru center is also coordinated with a η-L bidentate ligand. The Ru-Ru distances fall in the range of 2.4560(9)-2.4771(4) Å. The investigation of the electronic spectra and vibrational frequencies as well as theoretical studies with density functional theory (DFT) reveal that compounds 1-10 are ESBO bimetallic species of d-d valence electron counts showing a σπδδ*π* electronic configuration. Varying -CH to -CF groups on the η-L bidentate ligands coordinating to the Ru(μ-OCR')(μ-OR)Ru core, and according to Raman spectrum measurements combined with theoretical calculations, the intense bands of compounds 1-10 appearing at ∼345 cm in the small-wavenumber region can be assigned to the stretching of the Ru-Ru single bond.
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