Examples of octahedral compounds are sulfur hexafluoride SF6 and molybdenum hexacarbonyl Mo(CO)6.

The term "octahedral" is used somewhat loosely by chemists, focusing on the geometry of the bonds to the central atom and not considering differences among the ligands themselves.

When two or more types of ligands (La, Lb, ...) are coordinated to an octahedral metal centre (M), the complex can exist as isomers.

One can see that octahedral coordination allows much greater complexity than the tetrahedron that dominates organic chemistry.

The term can also refer to octahedral influenced by the Jahn–Teller effect, which is a common phenomenon encountered in coordination chemistry.

Many metal pentahalide and pentaalkoxide compounds exist in solution and the solid with bioctahedral structures.

The interconversion of Δ- and Λ-complexes, which is usually slow, is proposed to proceed via a trigonal prismatic intermediate, a process called the "Bailar twist".

On the other hand, the energy of the dxz, dxy, and dyz orbitals, the so-called t2g set, are stabilized.

The energy gap is labeled Δo, which varies according to the number and nature of the ligands.

When an anionic ligand replaces a coordinated water molecule the reaction is called an anation.

The reverse reaction, water replacing an anionic ligand, is called aquation.

Addition of concentrated HCl converts the aquo complex back to the chloride, via an anation process.