Dmg And The Spectrochemical Series

A spectrochemical series is a list of ligands ordered on ligand strength and a list of metal ions based on oxidation number, group and its identity. In crystal field theory, 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.

A spectrochemical series is a list of ligands ordered on ligand strength and a list of metal ions based on oxidation number, group and its identity. In crystal field theory, ligands modify the difference in energy between the d orbitals 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.

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Spectrochemical series. The spectrochemical series in itself is already a convolute of multiple different effects and it is defined for octahedral complexes. However, if we stick to small regions of it, we can make out trends based on general observations.
The electrochemical series is built up by arranging various redox equilibria in order of their standard electrode potentials (redox potentials). The most negative E° values are placed at the top of the electrochemical series, and the most positive at the bottom.

Spectrochemical series of ligands[edit]

The spectrochemical series was first proposed in 1938 based on the results of absorption spectra of cobalt complexes.^[1]

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

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I⁻ < Br⁻ < S²⁻ < SCN⁻ (S–bonded) < Cl⁻< N₃⁻ < F⁻< NCO⁻ < OH⁻ < C₂O₄²⁻ < O²⁻< H₂O < acac⁻ (acetylacetonate) < NCS⁻ (N–bonded) < CH₃CN < gly (glycine) < py (pyridine) < NH₃ < en (ethylenediamine) < bipy (2,2'-bipyridine) < phen (1,10-phenanthroline) < NO₂⁻ < PPh₃ < CN⁻ < CO

Weak field ligand: H₂O,F-,Cl-,OH-Strong field ligand: 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, keep in mind that 'the spectrochemical series is essentially backwards from what it should be for a reasonable prediction based on the assumptions of crystal field theory.'^[2] 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. Some, like NH₃, are σ bond donors only, with no orbitals of appropriate symmetry for π bonding interactions. Bonding by these ligands to metals is relatively simple, using only the σ bonds to create relatively weak interactions. Another example of a σ bonding ligand would be ethylenediamine, however ethylenediamine has a stronger effect than ammonia, generating a larger ligand field split, Δ.

Ligands that have occupied p orbitals are potentially π donors. These types of ligands tend to donate these electrons to the metal along with the σ bonding electrons, exhibiting stronger metal-ligand interactions and an effective decrease of Δ. Most halide ligands as well as OH⁻ are primary examples of π donor ligands.

When ligands have vacant π* and d orbitals of suitable energy, there is the possibility of pi backbonding, and the ligands may be π acceptors. This addition to the bonding scheme increases Δ. Ligands that do this very effectively include CN⁻, CO, and many others.^[3]

Spectrochemical series of metals[edit]

The metal ions can also be arranged in order of increasing Δ, and this order is largely independent of the identity of the ligand.^[4]

Mn²⁺ < Ni²⁺ < Co²⁺ < Fe²⁺ < V²⁺ < Fe³⁺ < Cr³⁺ < V³⁺ < Co³⁺ How to fix corrupted dmg file manager.

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.^[4]

Spectrochemical Series Explained