Abstract
A new synthetic route to generate tetraphenylporphyrin ruthenium(II) thiocarbonyl complexes of the general formula Ru 11(Por)(CS)L has been developed and the chemistry and electrochemistry of these complexes have been studied. [Ru IV(Por)(EtO)] 2O has been applied as a convenient starting material for ligand incorporation using carbon disulphide, thiophosgene and benzyl trichloromethyl thioether as thiocarbonyl precursors in the reducing medium. The RuCS bond is very strong and resistant to nucleophilic replacement. Thiocarbonyl and carbonyl ruthenium(II) porphyrin complexes reveal essential similarity as far as chemical and electrochemical properties are concerned, with the exception of the internal reactivity of the thiocarbonyl ligand. One-electron oxidation of [Ru(Por)(CS)(EtOH)] led to the formation of the respective π-cation radical characterized by visible, IR and 1H NMR spectroscopy.
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