Geometric and electronic structure of [{Cu(MeAN)}2(μ-η2:η2(O2(2-)))]2+ with an unusually long O-O bond: O-O bond weakening vs activation for reductive cleavage.

Journal of the American Chemical Society
Ga Young ParkKenneth D Karlin

Abstract

Certain side-on peroxo-dicopper(II) species with particularly low ν(O-O) (710-730 cm(-1)) have been found in equilibrium with their bis-μ-oxo-dicopper(III) isomer. An issue is whether such side-on peroxo bridges are further activated for O-O cleavage. In a previous study (Liang, H.-C., et al. J. Am. Chem. Soc.2002, 124, 4170), we showed that oxygenation of the three-coordinate complex [Cu(I)(MeAN)](+) (MeAN = N-methyl-N,N-bis[3-(dimethylamino)propyl]amine) leads to a low-temperature stable [{Cu(II)(MeAN)}(2)(μ-η(2):η(2)-O(2)(2-))](2+) peroxo species with low ν(O-O) (721 cm(-1)), as characterized by UV-vis absorption and resonance Raman (rR) spectroscopies. Here, this complex has been crystallized as its SbF(6)(-) salt, and an X-ray structure indicates the presence of an unusually long O-O bond (1.540(5) Å) consistent with the low ν(O-O). Extended X-ray absorption fine structure and rR spectroscopic and reactivity studies indicate the exclusive formation of [{Cu(II)(MeAN)}(2)(μ-η(2):η(2)-O(2)(2-))](2+) without any bis-μ-oxo-dicopper(III) isomer present. This is the first structure of a side-on peroxo-dicopper(II) species with a significantly long and weak O-O bond. DFT calculations show that the weak O-O bond results from strong...Continue Reading

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Nov 28, 2013·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Domenick F Leto, Timothy A Jackson
Jul 25, 2015·Accounts of Chemical Research·Joan Serrano-PlanaMiquel Costas
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