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

doi:10.1021/ja503629r

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

Chemistry (Twin Cities)

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Abstract

A macrocyclic ligand (L^4-) 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[L₂Cu₄(μ₄-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 language	English (US)
Pages (from-to)	7269-7272
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	136
Issue number	20
DOIs	https://doi.org/10.1021/ja503629r
State	Published - May 21 2014

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

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[L2Cu4(μ4-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.",

author = "Halvagar, {Mohammad Reza} and Pavlo Solntsev and Hyeongtaek Lim and Britt Hedman and Hodgson, {Keith O.} and Solomon, {Edward I.} and Chris Cramer and Tolman, {William B}",

year = "2014",

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T1 - Hydroxo-bridged dicopper(II,III) and -(III,III) complexes

T2 - Models for putative intermediates in oxidation catalysis

AU - Halvagar, Mohammad Reza

AU - Solntsev, Pavlo

AU - Lim, Hyeongtaek

AU - Hedman, Britt

AU - Hodgson, Keith O.

AU - Solomon, Edward I.

AU - Cramer, Chris

AU - Tolman, William B

PY - 2014/5/21

Y1 - 2014/5/21

N2 - 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[L2Cu4(μ4-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.

AB - 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[L2Cu4(μ4-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.

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 20

ER -

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

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