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Intermediates in Reactions of Copper(I) Complexes with N-Oxides

Recent research from the research group of Professor Bill Tolman.

In a paper just published (Inorg. Chem. 2009, 48, 6323-6325) and featured on the cover of the journal issue (reproduced below), graduate students Sungjun Hong and Aalo Gupta in the laboratory of Professor William Tolman report new results of the reactions of copper(I) complexes with N-oxides that depend on the nature of the supporting ligand. Key findings include the isolation of novel, stable copper(I) N-oxide adducts and the observation of oxo transfer to a copper(I) complex to yield a bis(μ-oxo)dicopper core. Whether adduct formation or oxo transfer occurs depends on the electron donating capabilities of the supporting ligand; when the ligand is "cold" (poor electron donor, with CF3 substituents), adduct formation occurs, but when the ligand is "hot" (strong electron donor), N-O bond scission and oxo transfer is observed. This work, which is supported by the NIH, provides important precedence for possible steps in the mechanisms of Cu/O-mediated reactions in biology and catalysis.


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