C–N Bond Cleavage of Anilines by a (Salen)ruthenium(VI) Nitrido Complex

Abstract

We report experimental and computational studies of the facile oxidative C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex. We provide evidence that the initial step involves nucleophilic attack of aniline at the nitrido ligand of the ruthenium complex, which is followed by proton and electron transfer to afford a (salen)ruthenium(II) diazonium intermediate. This intermediate then undergoes unimolecular decomposition to generate benzene and N2.

Properties and reactivity of μ-nitrido-bridged dimetal porphyrinoid complexes: how does ruthenium compare to iron?

“…As such the reactivity with substrates is expected to take place on the doublet spin state only and the oxidants will react through single-state-reactivity [51,52] selectively. Mononuclear [53][54][55]. Indeed previous studies on mononuclear Ru IV =O complexes showed the high-spin states to be considerably higher in energy than the lower spin states [56] in agreement with what is seen here.…”

Kinetics and Mechanism of the Reaction of a Ruthenium(VI) Nitrido Complex with HSO3− and SO32− in Aqueous Solution

“…This complex is found to be highly electrophilic/oxidizing. For example, it readily undergoes C−N bond cleavage of aniline, C−H bond activation of alkanes, aziridination of alkenes, and functionalization of alkynes in non‐aqueous solvents.…”

Editorial of Special Issue Ruthenium Complex: The Expanding Chemistry of the Ruthenium Complexes

“…Schiff-base (e.g. Salen) Ru-complexes enable versatile asymmetric catalysis for a range of chemical transformations, especially for carbene, nitrene, and oxene transfer reactions [11,146,215,216]. Complexes of this class reportedly serve as catalysts for oxidation/epoxidation, with chiral Ru-complexes such as Ru-porphyrin, desymmetric Ru-Schiff base and Ru-bisamide complexes being employed in asymmetric epoxidation.…”