Synthesis, characterization and electrochemistry of bis(3-aryl-6,6-dimethylcyclohexadienyl)ruthenium complexes |
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Authors: | Rein U. Kirss Alexandra Henriksen William Feighery |
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Affiliation: | a Department of Chemistry, Northeastern University, Boston, MA 02115, United States b Department of Chemistry, Indiana University-South Bend, South Bend, IN 46634, United States |
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Abstract: | Five bis(3-aryl-6,6-dimethylcyclohexadienyl)ruthenium complexes (4a-4e) are prepared by reactions between di-μ-chlorodichlorobis[(1-3η:6-8η)-2,7-dimethyl-octadienyl]diruthenium and the corresponding dienes. The larger aryl substituents increase the barrier to rotation in 4a-4e relative to bis(3-methyl-6,6-cyclohexadienyl)ruthenium (5b). The activation parameters were determined by line-shape analysis for the exchange process in 4a: ΔG† (183 K), 8.0 ± 0.2 kcal/mol; ΔH†, 10.3 kcal/mol; and ΔS†, 13 cal/mol/K. The electronic effect of the aryl substituents on the cyclohexadienyl ligand on the oxidation potential of the complex are compared to the effect of methyl substituents. |
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Keywords: | Open ruthenocenes Electrochemistry Cyclohexadienyl complexes |
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