Oxo-transfer reaction from a bis(μ-oxo)dicopper(III) complex to sulfides

Masayasu Taki, Shinobu Itoh, Shunichi Fukuzumi

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Oxygenation of sulfides to the corresponding sulfoxides by a distinct bis(μ-oxo)dicopper(III) complex has been accomplished for the first time using 2-(2-pyridyl)ethylamine derivative LPy1Bz (N-ethylN-[2-(2-pyridyl)ethyl]-α,α-dideuteriobenzylamine) as the supporting ligand. Detailed kinetic analysis has indicated that the reaction consists of two distinct steps, where the first quick process is association of the substrate to the bis(μ-oxo)dicopper(III) complex (k1) and the second slow process is intramolecular oxygen atom transfer from the copper-oxo species to the substrate in the associated complex (k2). The rate constant k2 of the second process is rather insensitive to the oxidation potential of the substrates, suggesting that the oxo-transfer reaction proceeds via a mechanism involving direct oxygen atom transfer rather than a mechanism involving electron transfer.

Original languageEnglish
Pages (from-to)998-1002
Number of pages5
JournalJournal of the American Chemical Society
Issue number6
StatePublished - 12 Feb 2002


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