A macrocyclic ligand (L<sup>4–</sup>) comprising two pyridine­(dicarboxamide) 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 LH<sub>4</sub> with base and Cu­(OAc)<sub>2</sub>·H<sub>2</sub>O yielded (Me<sub>4</sub>N)<sub>2</sub>[L<sub>2</sub>Cu<sub>4</sub>(μ<sub>4</sub>-O)] (<b>1</b>) or (Me<sub>4</sub>N)­[LCu<sub>2</sub>(μ-OH)] (<b>2</b>), depending on conditions. Complex <b>2</b> 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)<sub>2</sub> species, respectively, that provide the first precedence for such moieties as oxidation catalysis intermediates

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oaioai:figshare.com:artic...Last time updated on 2/12/2018

This paper was published in FigShare.

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