The First 85 Years of C-Nitroso Compounds: A Survey of the Salient Features

Abstract

In this account we trace the development of the structural chemistry of C-nitroso compounds from 1874, the year in which research into these compounds began. From the beginning, the colors displayed by these compounds (blue, blue-green, white) fascinated researchers, and it was soon realized that dimerization of the compounds could account for the white color of the solids. Extensive synthetic and reactive studies of the monomeric compounds resulted, and although some attention was directed to the structure of the dimers, both experimental and theoretical tools for this were limited. In the 1920s and 1930s electronic theories of valency were applied to nitroso compounds aided by dipole moment measurements. Systematic crystallographic and spectroscopic studies were employed from 1948 onwards. The early widespread belief that primary and secondary nitrosoalkanes were too unstable to isolate (due to isomerization to oximes) was overcome by successful syntheses of these compounds. The example of C-nitroso compounds illustrates the interplay of theory and experiment throughout the period 1874–1959.