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.