The reaction of a polypyridyl-ruthenium(II) acetonitrile complex and an iodosylarene compound was examined by 1H NMR spectroscopy in deuterated dimethylsulfoxide (d-DMSO). Surprisingly, the products of the reaction suggested that oxygen atom transfer to the acetonitrile ligand occurred first, followed by imido group transfer to the solvent. The product of imido group transfer to d-DMSO, a sulfoximine, was confirmed by independently synthesizing the product and comparing the 1H and 13C NMR spectra. The kinetics of the reaction were also explored to determine the mechanism of the reaction, and a reactive ruthenium(IV)imido was postulated as the intermediate.

Oxidation of a coordinated nitrile ligand and imido transfer to the solvent

ACS Fall 2021

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