Synthesis and characterization of lithium oxonitrate (LiNO).

Christopher H Switzer, Thomas W Miller, Patrick J Farmer, Jon M Fukuto

Index: J. Inorg. Biochem. 118 , 128-33, (2013)

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Abstract

The oxonitrate(1-) anion (NO(-)), the one-electron reduction product of nitric oxide and conjugate base of HNO, has not been synthesized and isolated due to the inherent reactivity of this anion. The large scale synthesis and characterization of a stable NO(-) salt is described here. The lithium salt of oxonitrate (LiNO) was formed by the deprotonation of N-hydroxybenzenesulfonamide with phenyllithium in aprotic, deoxygenated conditions. LiNO exhibited antiferromagnetic paramagnetism as determined by SQUID magnetometry, consistent with a triplet ground state of NO(-). LiNO reacted with HCl to yield nitrous oxide consistent with HNO formation and dimerization. LiNO consumed O(2) in a pH-dependent manner to initially produce peroxynitrite and eventually nitrite. Consistent with the reduction potential of NO, LiNO exhibited an oxidation potential of approximately +0.80 V as determined by reactions with a series of viologen electron acceptors. LiNO also reacted with ferric tetraphenylporphyrin chloride (Fe(TPP)Cl), potassium tetracyanonickelate (K(2)Ni(CN)(4)) and nitrosobenzene in a manner that is identical to other HNO/NO(-) donors. We conclude that the physical and chemical characteristics of LiNO are indistinguishable from the experimentally and theoretically derived data on oxonitrate (1-) anion. The bulk synthesis and isolation of a stable (3)NO(-) salt described here allow the chemical and physical properties of this elusive nitrogen oxide to be thoroughly studied as this once elusive nitrogen oxide is now attainable.Published by Elsevier Inc.