Catalytic oxidation of alkanes by a (salen)osmium(vi) nitrido complex using H2O2 as the terminal oxidant

Abstract

The osmium(VI) nitrido complex, [Os^VI(N)(L)(CH₃OH)]⁺ (1, L = N,N′-bis(salicylidene)-o-cyclohexyldiamine dianion) is an efficient catalyst for the oxidation of alkanes under ambient conditions using H₂O₂ as the oxidant. Alkanes are oxidized to the corresponding alcohols and ketones, with yields up to 75% and turnover numbers up to 2230. Experimental and computational studies are consistent with a mechanism that involves O-atom transfer from H₂O₂ to [Os^VI(N)(L)]⁺ to generate an [Os^VIII(N)(O)(L)]⁺ active intermediate.