[CpRu( s-indacene)RuCp] and [CpRu( s-indacene)RuCp] +: Experimental and theoretical findings concerning the electronic structure of neutral and mixed valence organometallic systems

• Published in: Polyhedron 2010-02, Vol.29 (3), p.1137-1143
• Main Authors: Mac-Leod Carey, D., Morales-Verdejo, C., Muñoz-Castro, A., Burgos, F., Abril, D., Adams, C., Molins, E., Cador, O., Chávez, I., Manríquez, J.M., Arratia-Pérez, R., Saillard, J.Y.
• Format: Article
• Language: English
• Subjects: Chemical Sciences; DFT; Electron transfer; Inorganic chemistry; Mixed valence; or physical chemistry; Organometallic; Ruthenium; s-Indacene; Theoretical and
• ISSN: 0277-5387; 0277-5387
• DOI: 10.1016/j.poly.2009.12.002

The synthesis of [{Cp*Ru} 2Ic′] ( 1, Ic′ = 2,4-diethyl-4,8-dimethyl- s-indacene) is reported. It was characterized by means of X-ray crystallography, NMR and CV experiments. The subsequent oxidation of 1 gives the mixed valence compound [{Cp*Ru} 2Ic′] + ( 2) which presents an intervalence band. DFT calculations for 1 and 2 are reported. Both experimental and theoretical facts show that the mixed valence system ( 2) can be classified as Class III. The reaction of 2,6-diethyl-4,8-dimethyl- s-indacenyl-dilithium (Li 2Ic′) with [Cp*RuCl] 4 gives the organometallic binuclear bis-pentamethylcyclopentadienyl-ruthenium- s-indacene complex, [{Cp*Ru} 2Ic′] ( 1, Ic′ = 2,4-diethyl-4,8-dimethyl- s-indacene), in high yields. The subsequent oxidation of 1 with a ferricinium salt ([Fc] +[BF 4] −) gives the mixed valence compound [{Cp*Ru} 2Ic′] +[BF 4] − ( 1 +). Compound 1 was structurally characterized by X-ray crystallography, finding that both {Cp*Ru} fragments are coordinated to opposite sites of the Ic′ ligand. The structural and electronic features of 1 and 1 + have been rationalized by Density Functional Theory (DFT) calculations, which suggest that both metallic centers get closer to the Ic′ and subtle electronic reorganizations occurs when chemical oxidation takes place. Cyclic voltammetry and ESR experiments suggest a high electronic interaction between the metallic centers mediated by the Ic′ bridging ligand. Time dependent DFT (TD-DFT) calculations were carried out to understand and assign the intervalence band present in the mixed-valent specie ( 1 +). The main achievement of this article is to feature the relationship of the experimental data with the computational results obtained with the Amsterdam Density Functional package (ADF). Both experimental and theoretical facts demonstrate that the mixed valence system ( 1 +) is a delocalized one, and it can be classified as a Class III system according to the Robin & Day classification.