Dinitroso and polynitroso compounds

Abstract

The growing interest in the chemistry of C-nitroso compounds (RN=O; R = alkyl or aryl group) is due in part to the recognition of their participation in various metabolic processes of nitrogen-containing compounds. C-Nitroso compounds have a rich organic chemistry in their own right, displaying interesting intra- and intermolecular dimerization processes and addition reactions with unsaturated compounds. In addition, they have a fascinating coordination chemistry. While most of the attention has been directed towards C-nitroso compounds containing a single -NO moiety, there is an emerging area of research dealing with dinitroso and polynitroso compounds. In this critical review, we present and discuss the synthetic routes and properties of these relatively unexplored dinitroso and polynitroso compounds, and suggest areas of further development involving these compounds. (126 references.).

On the mechanism of formation and spectral properties of radical anions generated by the reduction of –[ReI(CO)3(5-nitro-1,10-phenanthroline)]+ and –[ReI(CO)3(3,4,7,8-tetramethyl-1,10-phenanthroline)]+ pendants in poly-4-vinylpyridine polymers

“…In fact, most of Ar-NO compounds exist in solution as equilibrium mixtures of the monomer with the dimer, Eq. (17) [53,54].…”

Aromatic C-Nitroso Compounds and Their Dimers: A Model for Probing the Reaction Mechanisms in Crystalline Molecular Solids

“…Aromatic dinitroso compounds, e.g., p-dinitrosobenzene, are prone to polymerization which makes them promising candidates for the building blocks of supramolecular architectures [37][38][39]. Hacker reported the first isolation of p-dinitrosobenzene by gas phase deposition on the cold surface at 10 K, and its subsequent spontaneous polymerization upon heating the film of monomer to 170 K [63].…”

“…Aromatic dinitroso compounds, e.g., p-dinitrosobenzene, are prone to polymerization which makes them promising candidates for the building blocks of supramolecular architectures [37][38][39].…”

“…Such a system is simple because it includes the formation and/or breaking of only one chemical bond between two nitrogen atoms during the dimerization of C-nitroso compounds to the Z-or E-azodioxy dimers, or their subsequent dissociation to the starting monomers (Scheme 1) [32][33][34][35][36][37][38][39]. Although most of the aromatic C-nitroso compounds appear as Z-or E-azodioxides in solid state, certain nitrosobenzene derivatives, such as those with strong electron-donating substituents in the para-position (e.g., p-nitrosoanisoles and p-nitrosoanilines), prefer a monomeric form.…”

Reactivity of 4-Nitrosoanilines Towards Dimeric Halogenido-bridged Complexes of Iridium(III) and Rhodium(III) of the Type [(η5- C5Me5)MX2]2

“…However, coordination to metal centers was not reported before 1907 [4]. Since these early attempts various synthetic routes to high-yield preparations of C-nitroso compounds were developed [5,6]. Current reviews show the constant interest in this field of research during the last decades [7].…”