A Ni(II) Knife for Oxygen

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Science  17 Jan 2003:
Vol. 299, Issue 5605, pp. 313
DOI: 10.1126/science.299.5605.313a

Aerobic oxidation of organic compounds can be catalyzed by a number of Pd(II) complexes, but few examples are known for the corresponding Ni(II) system in the absence of large biomimetic ligands. Dible and Sigman show that a Ni(II) complex containing allyl chloride and N-heterocyclic carbene ligands reacts stoichiometrically with oxygen to yield aldehydes and ketones (derived from the allyl moiety) as well as a nickel dimer bridged by hydroxyl groups. The authors propose a mechanism in which O2 binds reversibly to the Ni(II) complex and decomposes it to one bound to a hydroxyl and an oxidized allyl species that is side-on bonded through its carbonyl group. Dimerization then liberates the oxidized organic species. Further study may lead to systems that perform this chemistry catalytically. — PDS

J. Am. Chem. Soc. 10.1021/ja0286876 (2002).

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