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Monocationic mu-diborolyl triple-decker complexes [CpCo(mu-1,3-C 3B2Me5)M(ring)]+: Synthesis, structures, and electrochemistry

Cationic triple-decker complexes with a bridging diborolyl ligand, [CpCo(mu-1,3-C3B2Me5)M(ring)]+ (M(ring) = CoCp (2a), CoCp* (2b), RhCp (3a), RhCp* (3b), IrCp (4a), IrCp* (4b), Ru(C6H6) (5a), Ru(p-MeC 6H4Pri) (5b), Ru(C6Me6) (5c), Ru(eta6-cycloheptatriene) (6)), were synthesized by reaction of CpCo(mu-1,3-C3B2Me5)Tl with [M(ring)Hal2]2. The structures of 2aBPh4, 2bPF6, 4aPF6, 5aOTf, and 5cPF6 were determined by X-ray diffraction. The electron-transfer ability of the complexes has been ascertained by electrochemical and spectroelectrochemical techniques. In general, they are able to shuttle reversibly in the sequence 2+/+/0/-, plausibly affording completely delocalized mixed-valence derivatives. DFT calculations revealed structural changes accompanying redox processes and satisfactorily predicted the potentials for the first reduction and first oxidation.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI