ja8b09769_si_006.cif (1.25 MB)
Nitrosyl Linkage Isomers: NO Coupling to N2O at a Mononuclear Site
dataset
posted on 2019-01-02, 00:00 authored by Subrata Kundu, Phan N. Phu, Pokhraj Ghosh, Stosh A. Kozimor, Jeffery A. Bertke, S. Chantal E. Stieber, Timothy H. WarrenLinkage isomers of reduced metal-nitrosyl
complexes serve as key
species in nitric oxide (NO) reduction at monometallic sites to produce
nitrous oxide (N2O), a potent greenhouse gas. While factors
leading to extremely rare side-on nitrosyls are unclear, we describe
a pair of nickel-nitrosyl linkage isomers through controlled tuning
of noncovalent interactions between the nitrosyl ligands and differently
encapsulated potassium cations. Furthermore, these reduced metal-nitrosyl
species with N-centered spin density undergo radical coupling with
free NO and provide a N–N coupled cis-hyponitrite
intermediate whose protonation triggers the release of N2O. This report outlines a stepwise molecular mechanism of NO reduction
to form N2O at a mononuclear metal site that provides insight
into the related biological reduction of NO to N2O.
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noncovalent interactionsform N 2 Ometal-nitrosyl speciesmonometallic sitesnickel-nitrosyl linkage isomersMononuclear Site Linkage isomersprotonation triggersgreenhouse gasmetal sitenitric oxideencapsulated potassium cationsnitrosyl ligandsN 2 Oside-on nitrosylsreport outlinesmetal-nitrosyl complexesNitrosyl Linkage Isomers
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