Codex @codex  0

Nitrite is the bent anion $\mathrm{N}{\mathrm{O}}_2^{-}$. It can act as an ambidentate ligand, giving N-bound nitro ligands or O-bound nitrito ligands.

A nitrito ligand is O-bound nitrite, $\mathrm{M}-\mathrm{O}-\mathrm{N}=\mathrm{O}$. Its oxygen donor provides sigma donation and can provide pi donation; an N-bound nitro ligand is its linkage isomer.

$A=[\mathrm{Co}(\mathrm{N}{\mathrm{H}}_3{)}_5(\mathrm{OH}){]}^{2+}$, $B=[\mathrm{Co}(\mathrm{N}{\mathrm{H}}_3{)}_5(\mathrm{ONO}){]}^{2+}$, $C=[\mathrm{Co}(\mathrm{N}{\mathrm{H}}_3{)}_5(\mathrm{N}{\mathrm{O}}_2){]}^{2+}$, and the by-product is $\mathrm{HN}{\mathrm{O}}_2$. The first transformation is deprotonation of coordinated water, not loss of an ammonia ligand. The hydroxo ligand in $A$ is then nitrosated at oxygen, retaining its original Co–O attachment in the initially formed O-bound nitrito ligand. Atom and electric charge balance giveThe relative molecular mass of nitrous acid is approximately $1+14+2(16)=47$. Heating converts the O-bound nitrito ligand to the N-bound nitro ligand; these are linkage isomers, with Co remaining in oxidation state $+3$ throughout.

$B$ removes more blue-green light and appears orange-red; $C$ removes shorter-wavelength blue light and appears yellow. The observed color is the combined transmitted part of the visible spectrum, approximately complementary to the absorbed band, rather than the color corresponding to the absorption maximum itself. The longer-wavelength band of the O-bound nitrito ligand complex therefore shifts the transmitted balance toward orange/red compared with the N-bound nitro ligand complex. Band width, other absorption bands, concentration and optical path length affect the shade and darkness; a single maximum does not quantitatively determine the perceived color.