Asymmetric oxygenation of a ruthenium dithiolate mimics the mixed sulfenato/sulfinato donor sets of nitrile hydratase and thiocyanate hydrolase.

The dithiolate complex (bmmp-TASN)RuPPh(3) reacts with O(2) under limiting conditions to yield the mixed sulfenato/sulfinato product (bmmp-O(3)-TASN)RuPPh(3) in 82% yield. Isotopic labeling studies confirm O(2) as the sole source of O atoms in the product complex. X-ray crystallographic studies reveal decreases in the Ru-S bond distances of 0.026(1) and 0.151(1) A for the sulfenato and sulfinato donors, respectively, and a 0.088(1) A increase in the Ru-PPh(3) bond distance upon oxygenation.