Inorganic Chemistry, Vol.49, No.12, 5344-5346, 2010
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 O-2 under limiting conditions to yield the mixed sulfenato/sulfinato product (bmmp-O-3-TASN)RuPPh3 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) angstrom for the sulfenato and sulfinato donors, respectively, and a 0.088(1) angstrom increase in the Ru-PPh3 bond distance upon oxygenation.