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NCERT Exemplar · Q43

Q.Match the complex ions given in Column I with the hybridisation and number of unpaired electrons given in Column II and assign the correct code:
Column I (Complex ion):
A. [Cr(H2O)6]3+[Cr(H_2O)_6]^{3+}
B. [Co(CN)4]2−[Co(CN)_4]^{2-}
C. [Ni(NH3)6]2+[Ni(NH_3)_6]^{2+}
D. [MnF6]4−[MnF_6]^{4-}
Column II (Hybridisation, number of unpaired electrons):
  1. dsp2dsp^2, 1
  2. sp3d2sp^3d^2, 5
  3. d2sp3d^2sp^3, 3
  4. sp3sp^3, 4
  5. sp3d2sp^3d^2, 2

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The key is to determine the oxidation state, electron configuration, and ligand field strength for each complex, then decide the hybridisation and count unpaired electrons. The correct matching is A-3, B-1, C-5, D-2.

Let’s unpack each complex one by one. The central idea is Crystal Field Theory — ligands create an electric field that splits the d-orbitals into two energy levels. Strong-field ligands (like CN⁻, NH₃) cause a large splitting, forcing electrons to pair up in lower orbitals (low spin). Weak-field ligands (like H₂O, F⁻) cause a small splitting, so electrons occupy all orbitals singly first (high spin). The hybridisation depends on how many empty orbitals are available after pairing.


1. Complex A: [Cr(H2O)6]3+[Cr(H_2O)_6]^{3+}

  • Oxidation state: Water is neutral, so Cr must be +3. Cr atomic number = 24, so Cr³⁺ has 24−3=2124 - 3 = 21 electrons. Electronic configuration of Cr: [Ar] 3d5 4s1[Ar]\,3d^5\,4s^1. Removing three electrons (first from 4s, then two from 3d) gives Cr³⁺: [Ar] 3d3[Ar]\,3d^3.
  • Ligand field: H₂O is a weak-field ligand (small splitting). So electrons remain unpaired as much as possible. With three d-electrons, they occupy three separate t₂g orbitals (Hund’s rule). No pairing occurs.
  • Hybridisation: The complex is octahedral (six ligands). The metal uses two d-orbitals (from inner 3d), one s, and three p orbitals — that’s d2sp3d^2sp^3 hybridisation. Since the d-orbitals used are from the inner shell (3d), it’s inner orbital complex.
  • Unpaired electrons: Three unpaired electrons.
Watch out

A common mistake is to think Cr³⁺ has 4s electrons left. Always remove 4s electrons first when forming cations.

So A matches with 3 (d2sp3d^2sp^3, 3).


2. Complex B: [Co(CN)4]2−[Co(CN)_4]^{2-}

  • Oxidation state: CN⁻ is −1 each, four of them give −4. Overall charge is −2, so Co must be +2. Co atomic number = 27, Co²⁺ has 27−2=2527 - 2 = 25 electrons. Co: [Ar] 3d7 4s2[Ar]\,3d^7\,4s^2, remove two 4s electrons → [Ar] 3d7[Ar]\,3d^7.
  • Ligand field: CN⁻ is a very strong-field ligand. It causes large splitting, forcing electrons to pair up. For a d⁷ system in a strong field, the configuration becomes (t2g)6(eg)1(t_{2g})^6 (e_g)^1 — six electrons paired in t₂g, one in e_g. That gives one unpaired electron.
  • Hybridisation: [Co(CN)4]2−[Co(CN)_4]^{2-} is a well-known exception to the usual four-coordinate geometry: because CN⁻ is such a strong-field ligand, the low-spin d7d^7 configuration is stabilised as square planar rather than tetrahedral, using dsp2dsp^2 hybridisation (dx2−y2d_{x^2-y^2} combined with one ss and two pp orbitals). This leaves one unpaired electron in another d-orbital.
  • Unpaired electrons: One.

So B matches with 1 (dsp2dsp^2, 1).

Tip

For [Co(CN)4]2−[Co(CN)_4]^{2-}, remember it’s square planar, not tetrahedral — a classic exam trap. The strong field of CN⁻ overrides the usual tetrahedral preference for four-coordinate Co²⁺.


3. Complex C: [Ni(NH3)6]2+[Ni(NH_3)_6]^{2+}

  • Oxidation state: NH₃ is neutral, so Ni is +2. Ni atomic number = 28, Ni²⁺ has 28−2=2628 - 2 = 26 electrons. Ni: [Ar] 3d8 4s2[Ar]\,3d^8\,4s^2, remove two 4s → [Ar] 3d8[Ar]\,3d^8. …

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