Notes. Geometric effects on the redox properties of complexes [RuX2(R2SO) n (R2S)4-n ] and the implications for oxidation catalysis
- 1 January 1991
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 1,p. 157-161
- https://doi.org/10.1039/dt9910000157
Abstract
The electrochemistry of ruthenium(II) complexes of the type [RuX2(R2SO)n(R2S)4-n](where n= 1–4) have been studied with examples for fourteen of the fifteen possible isomers for this system. Cyclic voltammograms in CH2Cl2 reveal that a plot of E½versus n is linear with a slope of +0.22 V, indicating that each replacement of a sulphoxide ligand with a thioether donor increases the energy of the highest occupied molecular orbital (dπ) by ca. 4.8 kcal (ca. 20.08 kJ). When n= 2 five different structural isomers are possible, all of which have been synthesized. Their E½ values range from + 0.72 to 1.42 V. Ligand-additivity theory provides a consistent rational for interpretation of the results. Catalytic studies are described which reveal that only one structure, all-trans-[RuX2(R2SO)2(R2S)2], is catalytically active for O2 oxidations of alcohol. A discussion of the relationship between structure and redox catalysis is included.Keywords
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