JEE MAIN - Chemistry (2025 - 22nd January Evening Shift - No. 4)

The correct order of the following complexes in terms of their crystal field stabilization energies is :
$\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_4\right]^{2+}<\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_6\right]^{2+}<\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_6\right]^{3+}<\left[\mathrm{Co}(\mathrm{en})_3\right]^{3+}$
$\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_4\right]^{2+}<\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_6\right]^{2+}<\left[\mathrm{Co}(\mathrm{en})_3\right]^{3+}<\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_6\right]^{3+}$
$\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_6\right]^{2+}<\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_6\right]^{3+}<\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_4\right]^{2+}<\left[\mathrm{Co}(\mathrm{en})_3\right]^{3+}$
$\left[\mathrm{Co}(\mathrm{en})_3\right]^{3+}<\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_6\right]^{3+}<\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_6\right]^{2+}<\left[\mathrm{Co}\left(\mathrm{NH}_3\right)_4\right]^{2+}$

Explanation

The crystal field stabilization energy (CFSE) of a complex depends on two main factors:

Charge/Oxidation State of the Central Metal Atom: Higher oxidation states generally lead to greater crystal field splitting energy (Δ).

Field Strength of the Ligand: Stronger field ligands also result in greater splitting. Additionally, chelating ligands typically increase the field strength.

For octahedral complexes, the CFSE is calculated as:

$ \text{CFSE} = [-0.4 \, t_{2g} + 0.6 \, e_g ] \, \Delta_\circ $

Considering the complexes:

$[\text{Co(en)}_3]^{3+}$:

Co exists as Co$^{3+}$ with electronic configuration $t_{2g}^6 e_g^0$.

CFSE = $-2.4 \, (\Delta_0)_1$.

$[\text{Co(NH}_3)_6]^{3+}$:

Co also as Co$^{3+}$ with $t_{2g}^6 e_g^0$.

CFSE = $-2.4 \, (\Delta_0)_2$.

$[\text{Co(NH}_3)_6]^{2+}$:

Co with Co$^{2+}$ configuration $t_{2g}^5 e_g^2$.

CFSE = $-0.8 \, (\Delta_0)_3$.

$[\text{Co(NH}_3)_4]^{2+}$:

Co as Co$^{2+}$ with different configuration $e^4 t_2^3$.

CFSE = $-1.2 \, \Delta_t$, where $\Delta_t = \frac{4}{9} (\Delta_0)_3$.

The order of crystal field splitting energies, based on our criteria, is:

$ \Delta_t < (\Delta_0)_3 < (\Delta_0)_2 < (\Delta_0)_1 $

Therefore, the CFSEs of these complexes compare as follows:

$[\text{Co(en)}_3]^{3+}$ has the highest CFSE due to the $\Delta_0$ of the strongest field ligand and oxidation state.

$[\text{Co(NH}_3)_6]^{3+}$ follows with similarly high CFSE due to Co$^{3+}$.

$[\text{Co(NH}_3)_6]^{2+}$ has a moderate CFSE.

$[\text{Co(NH}_3)_4]^{2+}$ has the lowest CFSE with $\Delta_t$.

This hierarchy of CFSE is determined by both the oxidation state of the cobalt metal and the field strength of the ligands involved.

Comments (0)

Advertisement