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Hydroxo-Bridged Dicopper(II,III) and -(III,III) Complexes: Models for Putative Intermediates in Oxidation Catalysis

Halvagar, M. R.; Solntsev, P. V.; Lim, H.; Hedman, B.; Hodgson, K. O.; Solomon, E. I.; Cramer, C. J.; Tolman, W. B.
J. Am. Chem. Soc. 2014, 9, 7269 (doi:10.1021/ja503629r).

A macrocyclic ligand (L4–) comprising two pyridine(dicaroxamide) donors was used to target reactive copper species relevant to proposed intermediates in catalytic hydrocarbon oxidations by particulate methane monooxygenase and heterogeneous zeolite systems. Treatment of LH4 with base and Cu(OAc)2•H2O yielded (Me4N)2[L2Cu44-O)] (1) or (Me4N)[LCu2(μ-OH)] (2), depending on conditions. Complex 2 was found to undergo two reversible 1-electron oxidations via cyclic voltammetry and low temperature chemical reactions. On the basis of spectroscopy and theory, the oxidation products were identified as novel hydroxo-bridged mixed-valent Cu(II)Cu(III) and symmetric Cu(III)2 species, respectively, that provide the first precedence for such moieties as oxidation catalysis intermediates.