Chlorosyl Nitrite (OClNO): An Elusive Intermediate in the Photochemistry of Nitryl Chloride
Jiyang Yu1, Yuyang Li1, Guorui Zhang1
1Department of Chemistry, Advanced Institute of Future Energy, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, State Key Laboratory of Porous Materials for Separation and Conversion, Fudan University, Shanghai 200433, China.
Abstract:
Nitryl chloride (ClNO2) is a reactive trace gas in the troposphere that plays an important role in atmospheric chlorine chemistry. Previous studies on the photochemistry of ClNO2 reveal dissociation and isomerization to cis- and trans-chlorine nitrite (ClONO); however, evidence for the formation of the high-energy isomeric chlorosyl nitrite (OClNO) remains controversial since its first claimed identification about 50 years ago. Here, we report the direct observation of the cis- and trans-conformers of OClNO in the photochemistry of ClNO2 in solid Ar-matrices at 10 K. In addition to the characterization of OClNO by using matrix-isolation IR (with 18O- and 15N-isotope labeling) and UV-vis spectroscopy, spontaneous trans → cis conformational conversion via quantum tunneling with further photoisomerization to ClONO has been observed. Our results underscore the role of OClNO as a potent intermediate in the atmospheric chlorine chemistry at low temperatures.
More Related Videos
Related Concept Videos
Preparation of Nitriles
Nitriles to Ketones: Grignard Reaction
The mechanism begins with a nucleophilic attack by the...
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Overview
The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by...
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
Nitriles to Carboxylic Acids: Hydrolysis


