An investigation into the unusual linkage isomerization and nitrite reduction activity of a novel tris(2-pyridyl) copper complex

Roger, I., Wilson, C. , Senn, H. M. , Sproules, S. and Symes, M. D. (2017) An investigation into the unusual linkage isomerization and nitrite reduction activity of a novel tris(2-pyridyl) copper complex. Royal Society Open Science, 4(8), 170593. (doi:10.1098/rsos.170593)

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Abstract

The copper-containing nitrite reductases (CuNIRs) are a class of enzymes that mediate the reduction of nitrite to nitric oxide in biological systems. Metal–ligand complexes that reproduce the salient features of the active site of CuNIRs are therefore of fundamental interest, both for elucidating the possible mode of action of the enzymes and for developing biomimetic catalysts for nitrite reduction. Herein, we describe the synthesis and characterization of a new tris(2-pyridyl) copper complex ([Cu1(NO2)2]) that binds two molecules of nitrite, and displays all three of the common binding modes for NO2−, with one nitrite bound in an asymmetric quasi-bidentate κ2-ONO manner and the other bound in a monodentate fashion with a linkage isomerism between the κ1-ONO and κ1-NO2 binding modes. We use density functional theory to help rationalize the presence of all three of these linkage isomers in one compound, before assessing the redox activity of [Cu1(NO2)2]. These latter studies show that the complex is not a competent nitrite reduction electrocatalyst in non-aqueous solvent, even in the presence of additional proton donors, a finding which may have implications for the design of biomimetic catalysts for nitrite reduction.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Wilson, Dr Claire and Sproules, Dr Stephen and Senn, Dr Hans and Symes, Dr Mark and Roger Barba, Isolda
Authors: Roger, I., Wilson, C., Senn, H. M., Sproules, S., and Symes, M. D.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Royal Society Open Science
Publisher:The Royal Society
ISSN:2054-5703
ISSN (Online):2054-5703
Published Online:16 August 2017
Copyright Holders:Copyright © 2017 The Authors
First Published:First published in Royal Society Open Science 4(8): 170593
Publisher Policy:Reproduced under a Creative Commons license
Data DOI:10.5525/gla.researchdata.416

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
714601Driving energetically uphill processes using metal-ligand coordination complexesMark SymesThe Royal Society (ROYSOC)UF150104CHEM - CHEMISTRY