Asymmetric Oxygenation of a Ruthenium Dithiolate Mimics the Mixed Sulfenato/Sulfinato Donor Sets of Nitrile Hydratase and Thiocyanate Hydrolase

The dithiolate complex (bmmp-TASN)RuPPh3 reacts with O2 under limiting conditions to yield the mixed sulfenato/sulfinato product (bmmp-O3-TASN)RuPPh3 in 82% yield. Isotopic labeling studies confirm O2 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) Å for the sulfenato and sulfinato donors, respectively, and a 0.088(1) Å increase in the Ru−PPh3 bond distance upon oxygenation.