Formation of a Ruthenium(V) - Imido Complex and the Reactivity in Substrate Oxidation in Water through the Nitrogen Non-Rebound Mechanism

A Ru^II - NH₃ complex, 2, was oxidized through a proton-coupled electron transfer (PCET) mechanism with a Ce^IV complex in water at pH 2.5 to generate a Ru^V=NH complex, 5. Complex 5 was characterized with various spectroscopies, and the spin state was determined by the Evans method to be S = 1/2. The reactivity of 5 in substrate C-H oxidation was scrutinized in acidic water, using water-soluble organic substrates such as sodium ethylbenzene-sulfonate (EBS), which gave the corresponding 1-phenylethanol derivative as the product. In the substrate oxidation, complex 5 was converted to the corresponding Ru^III - NH₃ complex, 3. The formation of 1-phenylethanol derivative from EBS and that of 3 indicate that complex 5 as the oxidant does not perform nitrogen-atom transfer, in sharp contrast to other high-valent metal-imido complexes reported so far. Oxidation of cyclobutanol by 5 afforded only cyclobutanone as the product, indicating that the substrate oxidation by 5 proceeds through a hydride-transfer mechanism. In the kinetic analysis on the C-H oxidation, we observed kinetic isotope effects (KIEs) on the C-H oxidation with use of deuterated substrates and remarkably large solvent KIE (sKIE) in D₂O. These positive KIEs indicate that the rate-determining step involves not only cleavage of the C-H bond of the substrate but also proton transfer from water molecules to 5. The unique hydride-transfer mechanism in the substrate oxidation by 5 is probably derived from the fact that the Ru^IV - NH₂ complex (4) formed from 5 by 1e^-/1H⁺ reduction is unstable and quickly disproportionates into 3 and 5.