Proton-Coupled-Electron Transfer Enhances the Electrocatalytic Reduction of Nitrite to NO in a Bioinspired Copper Complex

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http://eprints.org/relation/isVersionOf https://researchdata.gla.ac.uk/id/document/1858 http://eprints.org/relation/isVolatileVersionOf https://researchdata.gla.ac.uk/id/document/1858 http://eprints.org/relation/isIndexCodesVersionOf https://researchdata.gla.ac.uk/id/document/1858 archive 6975 disk0/00/00/05/90 2018-03-14 11:22:06 2025-05-21 12:11:28 2018-03-14 11:22:06 data_collection show Cioncoloni Giacomo 42049 Roger Isolda Wilson Claire 32950 0000-0002-0090-5374 Sproules Stephen 30520 0000-0003-3587-0375 Symes Mark 15851 0000-0001-8067-5240 Wheatley Paul S. EaStCHEM School of Chemistry, University of St Andrews, Purdie Building, St Andrews, KY16 9ST, United Kingdom Morris Russell EaStCHEM School of Chemistry, University of St Andrews, Purdie Building, St Andrews, KY16 9ST, United Kingdom glaresearchdata:2018-03-14-590 Proton-Coupled-Electron Transfer Enhances the Electrocatalytic Reduction of Nitrite to NO in a Bioinspired Copper Complex pub 30101000 The selective and efficient electrocatalytic reduction of nitrite to nitric oxide (NO) is of tremendous importance, both for the development of NO-release systems for biomedical applications and for the removal of nitrogen oxide pollutants from the environment. In nature, this transformation is mediated by (amongst others) enzymes known as the copper-containing nitrite reductases. The development of synthetic copper complexes that can reduce nitrite to NO has therefore attracted considerable interest. However, there are no studies describing the crucial role of proton-coupled-electron transfer during nitrite reduction when using such synthetic complexes. Herein, we describe the synthesis and characterization of two previously unreported Cu complexes (3 and 4) for the electrocatalytic reduction of nitrite to NO, in which the role of proton-relaying units in the secondary coordination sphere of the metal can be probed. Complex 4 bears a pendant carboxylate group in close proximity to the copper center, whilst complex 3 lacks such functionality. Our results suggest that complex 4 is twice as effective an electrocatalyst for nitrite reduction than is complex 3, and that complex 4 is the best copper-based molecular electrocatalyst for this reaction yet discovered. The differences in reactivity between 3 and 4 are probed using a range of electrochemical, spectroscopic and computational methods, which shed light on the possible catalytic mechanism of 4 and implicate the proton-relaying ability of its pendant carboxylate group in the enhanced reactivity that this complex displays. These results highlight the critical role of proton-coupled-electron transfer in the reduction of nitrite to NO and have important implications for the design of biomimetic catalysts for the selective interconversions of the nitrogen oxides. 2018-03-14 published University of Glasgow 10.5525/gla.researchdata.590 Spreadsheet Text University of Glasgow 62131 1 Upgrading the small scale equipment base for early career researchers in the engineering and physical sciences Miles Padgett Engineering and Physical Sciences Research Council (EPSRC) EP/K031732/1 S&E P&A - PHYSICS & ASTRONOMY 71460 1 Driving energetically uphill processes using metal-ligand coordination complexes Mark Symes The Royal Society (ROYSOC) UF150104 CHEM - CHEMISTRY FALSE English http://dx.doi.org/10.1021/acscatal.8b00361 article 2028-03-14 R FALSE FALSE Proton-coupled electron transfer enhances the electrocatalytic reduction of nitrite to no in a bioinspired copper complex http://eprints.gla.ac.uk/id/eprint/161720