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

Article abstract of DOI:10.1021/jacs.9b07286

A cuprous chelate bearing a secondary sphere hydrogen bonding functionality, [(PV-tmpa)Cu^I]⁺, 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.

Full text of DOI:10.1021/jacs.9b07286

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Communication
Copper(I) Complex Mediated Nitric Oxide Reductive Coupling: Ligand
Hydrogen Bonding Derived Proton Transfer Promotes N2O(g) Release
Gayan B. Wijeratne, Mayukh Bhadra, Maxime A. Siegler, and Kenneth D. Karlin
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b07286 • Publication Date (Web): 17 Oct 2019
Downloaded from pubs.acs.org on October 20, 2019
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Copper(I) Complex Mediated Nitric Oxide Reductive Coupling: Ligand
Hydrogen Bonding Derived Proton Transfer Promotes N2O(g) Release
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Cu-only NOR model – Intramolecular H+ transfer
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DFT Optimized
H-bonded Hyponitrite Intermediate
(L)CuI complex
(L’)CuII product
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