JEE MAIN - Chemistry (2025 - 2nd April Evening Shift - No. 17)
Explanation
Determine the oxidation state of manganese in $$\left[\mathrm{MnCl}_6\right]^{3-}:$$
Chloride (Cl⁻) has a charge of -1.
With six chloride ions, the total charge contributed by the ligands is $$6(-1) = -6.$$
Let the oxidation state of Mn be $$x.$$ Then:
$$x - 6 = -3 \quad \Longrightarrow \quad x = +3.$$
So, manganese is in the +3 oxidation state.
Find the d-electron count for Mn(III):
The neutral manganese atom has the electronic configuration $$[\mathrm{Ar}]\, 3d^5 4s^2.$$
Removing three electrons (first from the 4s, then from the 3d) gives:
$$\mathrm{Mn}^{3+} : [\mathrm{Ar}]\, 3d^4.$$
Therefore, Mn(III) is a $$d^4$$ system.
Predict the spin state in an octahedral complex:
Chloride (Cl⁻) is a weak-field ligand, meaning it produces a relatively small crystal field splitting ($$\Delta_o$$).
When $$\Delta_o$$ is small, the pairing energy is higher than $$\Delta_o,$$ so electrons prefer to remain unpaired.
For a $$d^4$$ configuration in a high-spin octahedral complex, the electrons will be distributed as:
Three electrons in the three $$t_{2g}$$ orbitals (one in each)
One electron in one of the $$e_g$$ orbitals
This results in a total of 4 unpaired electrons, making the complex paramagnetic.
Determine the type of hybridization:
In octahedral complexes, the two common hybridizations are:
$$d^2sp^3$$ (inner orbital complex), typically seen in low-spin complexes where inner 3d orbitals are available because the electrons are paired.
$$sp^3d^2$$ (outer orbital complex), seen in high-spin complexes where the inner $$3d$$ orbitals are occupied by unpaired electrons.
Since $$\left[\mathrm{MnCl}_6\right]^{3-}$$ is high-spin (because of Cl⁻ being a weak-field ligand), the inner 3d orbitals are not available for hybridization.
Therefore, the complex uses the outer orbitals (the 4s, 4p, and 4d orbitals), leading to an $$sp^3d^2$$ hybridization.
Conclusion:
The hybridization of $$\left[\mathrm{MnCl}_6\right]^{3-}$$ is $$sp^3d^2.$$
It is paramagnetic with four unpaired electrons.
Thus, the correct answer is:
Option A: $$sp^3d^2$$, paramagnetic with four unpaired electrons.
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