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

[Image: see text] 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 LH(4) wi...

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Autores principales: Halvagar, Mohammad Reza, Solntsev, Pavlo V., Lim, Hyeongtaek, Hedman, Britt, Hodgson, Keith O., Solomon, Edward I., Cramer, Christopher J., Tolman, William B.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4046753/
https://www.ncbi.nlm.nih.gov/pubmed/24821432
http://dx.doi.org/10.1021/ja503629r
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author Halvagar, Mohammad Reza
Solntsev, Pavlo V.
Lim, Hyeongtaek
Hedman, Britt
Hodgson, Keith O.
Solomon, Edward I.
Cramer, Christopher J.
Tolman, William B.
author_facet Halvagar, Mohammad Reza
Solntsev, Pavlo V.
Lim, Hyeongtaek
Hedman, Britt
Hodgson, Keith O.
Solomon, Edward I.
Cramer, Christopher J.
Tolman, William B.
author_sort Halvagar, Mohammad Reza
collection PubMed
description [Image: see text] 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 LH(4) with base and Cu(OAc)(2)·H(2)O yielded (Me(4)N)(2)[L(2)Cu(4)(μ(4)-O)] (1) or (Me(4)N)[LCu(2)(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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spelling pubmed-40467532015-05-12 Hydroxo-Bridged Dicopper(II,III) and -(III,III) Complexes: Models for Putative Intermediates in Oxidation Catalysis Halvagar, Mohammad Reza Solntsev, Pavlo V. Lim, Hyeongtaek Hedman, Britt Hodgson, Keith O. Solomon, Edward I. Cramer, Christopher J. Tolman, William B. J Am Chem Soc [Image: see text] 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 LH(4) with base and Cu(OAc)(2)·H(2)O yielded (Me(4)N)(2)[L(2)Cu(4)(μ(4)-O)] (1) or (Me(4)N)[LCu(2)(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. American Chemical Society 2014-05-12 2014-05-21 /pmc/articles/PMC4046753/ /pubmed/24821432 http://dx.doi.org/10.1021/ja503629r Text en Copyright © 2014 American Chemical Society
spellingShingle Halvagar, Mohammad Reza
Solntsev, Pavlo V.
Lim, Hyeongtaek
Hedman, Britt
Hodgson, Keith O.
Solomon, Edward I.
Cramer, Christopher J.
Tolman, William B.
Hydroxo-Bridged Dicopper(II,III) and -(III,III) Complexes: Models for Putative Intermediates in Oxidation Catalysis
title Hydroxo-Bridged Dicopper(II,III) and -(III,III) Complexes: Models for Putative Intermediates in Oxidation Catalysis
title_full Hydroxo-Bridged Dicopper(II,III) and -(III,III) Complexes: Models for Putative Intermediates in Oxidation Catalysis
title_fullStr Hydroxo-Bridged Dicopper(II,III) and -(III,III) Complexes: Models for Putative Intermediates in Oxidation Catalysis
title_full_unstemmed Hydroxo-Bridged Dicopper(II,III) and -(III,III) Complexes: Models for Putative Intermediates in Oxidation Catalysis
title_short Hydroxo-Bridged Dicopper(II,III) and -(III,III) Complexes: Models for Putative Intermediates in Oxidation Catalysis
title_sort hydroxo-bridged dicopper(ii,iii) and -(iii,iii) complexes: models for putative intermediates in oxidation catalysis
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4046753/
https://www.ncbi.nlm.nih.gov/pubmed/24821432
http://dx.doi.org/10.1021/ja503629r
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