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Nitrosyl Linkage Isomers: NO Coupling to N2O at a Mononuclear Site
Subrata Kundu1,2, Phan N Phu3, Pokhraj Ghosh1
1Department of Chemistry , Georgetown University , Box 571227-1227, Washington , D. C. 20057 , United States.
Abstract:
Linkage 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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