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Concept
Spectrochemical series
Summary
A spectrochemical series is a list of ligands ordered by ligand "strength", and a list of metal ions based on oxidation number, group and element. For a metal ion, the ligands modify the difference in energy Δ between the d orbitals, called the ligand-field splitting parameter in ligand field theory, or the crystal-field splitting parameter in crystal field theory. The splitting parameter is reflected in the ion's electronic and magnetic properties such as its spin state, and optical properties such as its color and absorption spectrum.
The spectrochemical series was first proposed in 1938 based on the results of absorption spectra of cobalt complexes.
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− (S–bonded) < Cl− < NO3– < N3− < F− < OH− < C2O42− < H2O < NCS− (N–bonded) < CH3CN < py (pyridine) < NH3 < en (ethylenediamine) < bipy (2,2'-bipyridine) < phen (1,10-phenanthroline) < NO2− (N–bonded) < PPh3 (Triphenylphosphine) < CN− < CO
Weak field ligands: H2O, F−, Cl−, OH−
Strong field ligands: CO, CN−, NH3, PPh3
Ligands arranged on the left end of this spectrochemical series are generally regarded as weaker ligands and cannot cause forcible pairing of electrons within the 3d level, and thus form outer orbital octahedral complexes that are high spin. 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 and hence are called low spin ligands.
However, it is known that "the spectrochemical series is essentially backwards from what it should be for a reasonable prediction based on the assumptions of crystal field theory." This deviation from crystal field theory highlights the weakness of crystal field theory's assumption of purely ionic bonds between metal and ligand.
The order of the spectrochemical series can be derived from the understanding that ligands are frequently classified by their donor or acceptor abilities.
Official source
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