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Chemistry Question 62 – JEE-MAIN 2025

The number of unpaired electrons responsible for the paramagnetic nature of the following complex species are respectively : [Fe(CN)6]3−, [FeF6]3−, [CoF6]3−, [Mn(CN)6]3−

First, find the oxidation state of the central metal atom in each complex and then determine its d-electron configuration.

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Ninja Strategy•Sequential Ligand Field Analysis

Determine the oxidation state and d-electron count for each metal, then apply Crystal Field Theory considering strong or weak field ligands sequentially to eliminate options.

Step 1: Determine oxidation state and d-electron count for each metal ion✦ Active

For each complex, calculate the oxidation state of the central metal atom and determine its d-electron configuration:

- For [Fe(CN)6]3−: Fe3+ (3d5)

- For [FeF6]3−: Fe3+ (3d5)

- For [CoF6]3−: Co3+ (3d6)

- For [Mn(CN)6]3−: Mn3+ (3d4)

Step 2: Apply Crystal Field Theory based on ligand strength to find unpaired electrons○ Expand

Consider the ligand field strength (strong field or weak field) and distribute the d-electrons into t2g and eg orbitals for octahedral complexes:

- **[Fe(CN)6]3−:** Fe3+ (3d5). CN− is a strong field ligand. Electrons pair up. Configuration: t2g5eg0. Number of unpaired electrons = 1.

- **[FeF6]3−:** Fe3+ (3d5). F− is a weak field ligand. Electrons do not pair up. Configuration: t2g3eg2. Number of unpaired electrons = 5.

- **[CoF6]3−:** Co3+ (3d6). F− is a weak field ligand. Electrons do not pair up. Configuration: t2g4eg2. Number of unpaired electrons = 4.

- **[Mn(CN)6]3−:** Mn3+ (3d4). CN− is a strong field ligand. Electrons pair up. Configuration: t2g4eg0. Number of unpaired electrons = 2.

💡 Teacher's Secret Hint

Remember that strong field ligands (like CN−) cause pairing, leading to low spin complexes, while weak field ligands (like F−) do not, leading to high spin complexes.

Step 3: Compile the results and select the correct option○ Expand

The number of unpaired electrons for the complexes [Fe(CN)6]3−, [FeF6]3−, [CoF6]3−, and [Mn(CN)6]3− are 1,5,4,2 respectively. This sequence matches option 4.

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