Linkage isomerism occurs when complexes have the same composition but an ambidentate ligand attaches through different atoms. N-bound and O-bound nitrite provide the classical example. This is a difference in attachment connectivity, rather than the different spatial arrangements of unchanged connectivity in stereoisomers.
Linkage isomerization changes which atom of an ambidentate ligand is bound to a central atom. Its rate depends on a reaction barrier, whereas the final equilibrium depends on relative free energies.
A linkage isomer is one member of a set exhibiting linkage isomerism, such as the N-bound or O-bound form of a coordinated nitrite.
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Linkage isomerism is a type of isomerism found in coordination compounds. It arises when a ligand can coordinate to a metal center in more than one way, leading to different structural arrangements. In linkage isomerism, the position of the binding site of a ligand changes. For example, some ligands contain multiple donor atoms, where only one of those atoms binds to the metal ion at a time.