A spectrochemical series is a list of ligand

Ligand

In coordination chemistry, a ligand is an ion or molecule that binds to a central metal atom to form a coordination complex. The bonding between metal and ligand generally involves formal donation of one or more of the ligand's electron pairs. The nature of metal-ligand bonding can range from...

s ordered on ligand strength and a list of metal ions based on oxidation number

Oxidation number

In coordination chemistry, the oxidation number of a central atom in a coordination compound is the charge that it would have if all the ligands were removed along with the electron pairs that were shared with the central atom. Oxidation numbers are often confused with oxidation states.The...

, group and its identity. In crystal field theory

Crystal field theory

Crystal field theory is a model that describes the electronic structure of transition metal compounds, all of which can be considered coordination complexes. CFT successfully accounts for some magnetic properties, colours, hydration enthalpies, and spinel structures of transition metal complexes,...

, ligands modify the difference in energy between the d orbitals (Δ) called the ligand-field splitting parameter for ligands or the crystal-field splitting parameter, which is mainly reflected in differences in color of similar metal-ligand complexes.

Spectrochemical series of ligands

A partial spectrochemical series listing of ligands from small Δ to large Δ is given below.   (for a table, see the ligand page)

I⁻ < Br⁻ < S²⁻ < SCN⁻

Thiocyanate

Thiocyanate is the anion [SCN]−. It is the conjugate base of thiocyanic acid. Common derivatives include the colourless salts potassium thiocyanate and sodium thiocyanate. Organic compounds containing the functional group SCN are also called thiocyanates...

 < Cl⁻ < NO₃⁻ < N₃⁻ < F⁻ < OH⁻ < C₂O₄²⁻ ≈ H₂O < NCS⁻

Isothiocyanate

Isothiocyanate is the chemical group –N=C=S, formed by substituting sulfur for oxygen in the isocyanate group. Many natural isothiocyanates from plants are produced by enzymatic conversion of metabolites called glucosinolates. These natural isothiocyanates, such as allyl isothiocyanate, are also...

 < CH₃CN < py (pyridine

Pyridine

Pyridine is a basic heterocyclic organic compound with the chemical formula C5H5N. It is structurally related to benzene, with one C-H group replaced by a nitrogen atom...

) < NH₃ < en (ethylenediamine) < bipy (2,2'-bipyridine

2,2'-Bipyridine

2,2'-Bipyridine is a organic compound with the formula . This colorless solid, commonly abbreviated bipy or bpy , is an important isomer of the bipyridine family. It is a bidentate chelating ligand, forming complexes with many transition metals...

) < phen (1,10-phenanthroline

Phenanthroline

Phenanthroline is a heterocyclic organic compound. As a bidentate ligand in coordination chemistry, it forms strong complexes with most metal ions...

) < NO₂⁻ < PPh₃ < CN⁻ ≈ CO

Ligands arranged on the left end of this spectrochemical series are generally regarded as weaker ligands and cannot cause forcible pairing of electrons within 3d level and thus form outer orbital octahedral complexes. On the other hand ligands lying at the right end are stronger ligands and form inner orbital octahedral complexes after forcible pairing of electrons within 3d level.

In fact, the spectrochemical series is essentially backwards from what it should be for a reasonable prediction based on the assumptions of crystal field theory.

Spectrochemical series of metals

The metal ions can also be arranged in order of increasing Δ, and this order is largely independent of the identity of the ligand.

Mn²⁺ < Ni²⁺ < Co²⁺ < Fe²⁺ < V²⁺ < Fe³⁺ < Cr³⁺ < V³⁺ < Co³⁺

In general, it is not possible to say whether a given ligand will exert a strong field or a weak field on a given metal ion. However, when we consider the metal ion, the following two useful trends are observed:

• Δ increases with increasing oxidation number, and
• Δ increases down a group.