Abstract
AbstractImido osmium(VIII) complexes are versatile oxidants for C−C double bond functionalisation. Despite their structural similarity with OsO4 their reactivity cannot always be compared with this seminal reagent. Detailed investigations including kinetic competition experiments are presented that uncover the electronic and steric preferences of osmium imido complexes. The different behaviour of OsO4 and its imido derivatives towards tertiary amines and diamines is clarified. Hammett correlation studies reveal that the reactivity spectrum of the respective oxidants ranges from a strongly electrophilic behaviour in the case of OsO4 to a rather nucleophilic character as encountered for OsO(NtBu)3. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
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