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.
Masitas
César A
CA
Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA.
Mashuta
Mark S
MS
Grapperhaus
Craig A
CA
D018360:Crystallography, X-Ray; D006836:Hydro-Lyases / Q000737:chemistry / Q000378:metabolism*; D006867:Hydrolases / Q000737:chemistry / Q000378:metabolism*; D008958:Models, Molecular; D018716:Molecular Mimicry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D012428:Ruthenium; D006867:Hydrolases; C074369:thiocyanate hydrolase; D006836:Hydro-Lyases; C048831:nitrile hydratase; D010100:Oxygen