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Discuss the chelate effect with an example. Explain the nature of bonding in \( [\text{Fe}(\text{CN})_6]^{4-} \) on the basis of valence bond theory. (2+2=4)

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Chelate effect = extra stability from ring-forming polydentate ligands (entropy driven), e.g. \( [Ni(en)_3]^{2+} \). For \( [Fe(CN)_6]^{4-} \): Fe is \( +2 \) (\( 3d^6 \)), strong-field \( CN^- \) pairs the electrons giving \( d^2sp^3 \), octahedral, diamagnetic.
Updated On: Jul 10, 2026
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Solution and Explanation

Step 1: What chelation means.
A ligand carrying more than one donor site can grip the metal at two points at once, like a claw (Greek 'chele' = claw). The resulting five or six membered ring locks the metal in place. Complexes built from such chelating ligands resist dissociation more strongly than those built from single-site ligands, and this enhanced stability is the chelate effect.

Step 2: Illustration.
Compare \([Ni(en)_3]^{2+}\) with \([Ni(NH_3)_6]^{2+}\). Replacing six \(NH_3\) by three \(en\) molecules releases extra species into solution, raising the entropy; the more positive \(\Delta S\) lowers \(\Delta G\), so the chelated complex has a larger stability constant.

Step 3: Charge balance for the iron complex.
In \([Fe(CN)_6]^{4-}\) each cyanide is \(-1\), so iron must be \(+2\). Thus we treat \(Fe^{2+}\): \(3d^6\) after removing the two \(4s\) electrons.

Step 4: Pairing under a strong ligand.
\(CN^-\) lies high in the spectrochemical series, so the ligand field is large enough to pair the \(3d\) electrons. The \(d^6\) set collapses into three fully paired \(3d\) orbitals, vacating two \(3d\) orbitals for bonding.

Step 5: Orbital picture and prediction.
Two vacant \(3d\) + one \(4s\) + three \(4p\) mix into six equivalent \(d^2sp^3\) hybrids pointing to the corners of an octahedron. Each accepts a lone pair from \(CN^-\). Because it uses inner \(d\) orbitals it is a low-spin (inner orbital) octahedral complex, and with no unpaired electron it is diamagnetic.
\[ \boxed{d^2sp^3,\ \text{octahedral, inner orbital, diamagnetic}} \]
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