Question
Question: Given the maximum absorption for \[d - d\]transition in \({[Ti{({H_2}O)_6}]^{3 + }}\)occurs at \(203...
Given the maximum absorption for d−dtransition in [Ti(H2O)6]3+occurs at 20300cm−1, predict where the peak (d−dtransition)will occur for [Ti(CN)6]3−and [Ti(Cl)6]3−respectively:
A)23000cm−1,32000cm−1 B)18000cm−1,21300cm−1 C)23000cm−1,17300cm−1 D)18000CM−1,17300cm−1
Solution
In a d−d transition, an electron in d orbital on the metal is excited by a photon to another d orbital of higher energy. In complexes of the transition metals, the d orbitals do not all have the same energy. In centrosymmetric complexes, d−d transitions are forbidden by the Laporte rule.
Complete answer:
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.
According to spectrochemical series:
Cl<H2O<CN−.
So, as the ligand field increases wave number also increases.
So, the correct answer is A)23000cm−1,32000cm−1
Additional information:
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 σbond donors only, with no orbitals of appropriate symmetry forπbonding interactions. Bonding by these ligands to metals is relatively simple, using only theσ bonds to create relatively weak interactions. Another example of a σbonding ligand would be ethylenediamine; however, ethylenediamine has a stronger effect than ammonia, generating a larger ligand field split.
Note:
The metal ions can also be arranged in order of increasing Δ, and this order is largely independent of the identity of the ligand. 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, Δ increases with increasing oxidation number, and Δ increases down a group.