36529-65-4Relevant academic research and scientific papers
Synthesis and characterization of lithium oxonitrate (LiNO)
Switzer, Christopher H.,Miller, Thomas W.,Farmer, Patrick J.,Fukuto, Jon M.
, p. 128 - 133 (2013/02/23)
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 O2 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 (K2Ni(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 3NO- 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.
Infrared spectrum of the hyponitrite dianion, N2O22-, isolated and insulated from stabilizing metal cations in solid argon
Andrews,Liang
, p. 1997 - 2002 (2007/10/03)
Ultraviolet irradiation of a rigid 7 K argon matrix containing alkali or alkaline earth metal atoms and (NO)2 isolated from each other by one or two layers of argon forms N2O22- dianions insulated from two M+ cations by argon atoms, and visible photolysis reverses this electron-transfer process likely involving the N2O2- anion intermediate. The isolated N2O22- dianion is identified from isotopic substitution and isotopic mixtures, which show that the new 1028.5 cm-1 metal independent absorption involves two equivalent NO subunits. DFT calculations predict a strong 1078.1 cm-1 fundamental for the Li(NO)2Li molecule and isotopic frequency ratios in excellent agreement with the observed values, which provides a model for the matrix dianion system. The spectrum of solid Na2N2-O2, exhibits a 1030 cm-1 infrared band, which strongly supports the present N2O22- dianion assignment. The electrostatic stabilization of N2O22-, which is probably unstable in the gas phase, is made possible by metal cations separated by one or two insulating layers of argon in the rigid 7 K matrix.
