Soluble [Rh2(μ-OOCCH3)2(dbbpy)2][BF4]n molecular wire and [Rh2(μ-OOCCH3)2(dbbpy)2L2]2+ complexes; dbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine: Synthesis and physicochemical characterization
Binuclear Rh(II) compounds [Rh2(μ-OOCCH3)2(dbbpy)2(H2O)2](CH3COO)2 (1) (dbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine), [Rh2(μ-OOCCH3)2(dbbpy)2(H2O)2](BF4)2·H2O·CH3CN (2), [Rh2(CH3COO)2(C18H24N2)2(CH3CN)2](BF4)2·4CH3CN (3) and {[Rh2(μ-OOCCH3)2(dbbpy)2][BF4]}n (4) have been synthesized and characterized with spectroscopic methods. Structure of complex 3 has been determined using X-ray crystallography. Rhodium atoms in compound 3 have distorted octahedral coordination with O and N atoms in equatorial positions and Rh atom and CH3CN molecule in axial coordination sites. Reduction of rhodium(II) compounds with aqueous 2-propanol leads to the formation of polymetallic compound {[Rh2(μ-OOCCH3)2(dbbpy)2][BF4]}n (4) containing [Rh2]3+ core. Compound 4shows strong antiferromagnetic properties, μ = 0.18–1.73 M.B. in the range 1.8–300 K, J = −597 cm−1. Electrochemistry of compounds 3 and 4 in CH3CN has been investigated. Compound 4 exhibits a poorly reversible oxidation system at E1/2 = −0.92 V (ΔEp = 0.19 V) and in solution in DMF is slowly oxidized to 3 even in total absence of oxygen. Complex 3 is irreversibly oxidized to Rh(III) compound at Epa = 1.48 V and irreversibly reduced at Epc = −1.02 V to lead to the unstable polynuclear complex 4 in CH3CN.
Références
- Titre
- Soluble [Rh2(μ-OOCCH3)2(dbbpy)2][BF4]n molecular wire and [Rh2(μ-OOCCH3)2(dbbpy)2L2]2+ complexes; dbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine: Synthesis and physicochemical characterization
- Type de publication
- Article de revue
- Année de publication
- 2010
- Auteurs
- Cwikowska, Magdalena, Pruchnik Florian P., Pavlyuk Oleksiy, Lafolet Frédéric, Chardon Sylvie, and Deronizer Alain
- Revue
- Polyhedron
- Volume
- 29
- Pagination
- 3059–3065
- ISSN
- 0277-5387