Hydroxo-bridged dicopper(II,III) and -(III,III) complexes: Models for putative intermediates in oxidation catalysis

Mohammad Reza Halvagar, Pavlo Solntsev, Hyeongtaek Lim, Britt Hedman, Keith O. Hodgson, Edward I. Solomon, Chris Cramer, William B Tolman

Research output: Contribution to journalArticle

47 Scopus citations

Abstract

A macrocyclic ligand (L4-) 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 LH4 with base and Cu(OAc)2·H2O yielded (Me4N) 2[L2Cu44-O)] (1) or (Me 4N)[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.

Original languageEnglish (US)
Pages (from-to)7269-7272
Number of pages4
JournalJournal of the American Chemical Society
Volume136
Issue number20
DOIs
StatePublished - May 21 2014

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