Copper(I) Complex Mediated Nitric Oxide Reductive Coupling: Ligand Hydrogen Bonding Derived Proton Transfer Promotes N2O(g) Release

A cuprous chelate bearing a secondary sphere hydrogen bonding functionality, [(PV-tmpa)­CuI]+, transforms •NO(g) to N2O(g) in high-yields in methanol. Ligand derived proton transfer facilitates N–O bond cleavage of a putative hyponitrite intermediate releasing N2O(g), underscoring the crucial balanc...

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Published inJournal of the American Chemical Society Vol. 141; no. 45; pp. 17962 - 17967
Main Authors Wijeratne, Gayan B, Bhadra, Mayukh, Siegler, Maxime A, Karlin, Kenneth D
Format Journal Article
LanguageEnglish
Published American Chemical Society 13.11.2019
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Summary:A cuprous chelate bearing a secondary sphere hydrogen bonding functionality, [(PV-tmpa)­CuI]+, transforms •NO(g) to N2O(g) in high-yields in methanol. Ligand derived proton transfer facilitates N–O bond cleavage of a putative hyponitrite intermediate releasing N2O(g), underscoring the crucial balance between H-bonding capabilities and acidities in (bio)­chemical •NO(g) coupling systems.
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Present Address Department of Chemistry, The University of Alabama at Birmingham, Birmingham, Alabama 35205, United States.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.9b07286