Skip to content
Question of 101

Q.Give reasons -

(a) [NiCl4]2- is paramagnetic while [Ni(CO)4] is diamagnetic though both are tetrahedral. Why? [2]
(b) Geometrical isomerism is not possible in tetrahedral complexes of the type [MA2X2], where M is central metal ion and A and X are different types of unidentate ligands. Why? [1]
(OR)
Discuss the geometry and magnetic character of the following coordination entities on the basis of Valence Bond Theory (VBT)-
(i) [Fe(CN)6]4-
(ii) [CoF6]3-
Uttarakhand UbseUttarakhand Board Intermediate (Class 12) 2025Subjective· 3mImportance★★★★★
0% · 0/101 Questions
🔒 Locked · start free trial →

You're viewing a preview — the full solution, concept, methods & PYQ mapping are locked.

Start your 14-day free trial to unlock the full solution →

Field strength of the ligand decides whether Ni's d-electrons pair up (CO, diamagnetic) or stay unpaired (Cl-, paramagnetic); tetrahedral geometry has no distinct cis/trans sites.

  1. [NiCl4]²⁻ vs [Ni(CO)4]: In [NiCl4]2−[NiCl_4]^{2-}, nickel is present as Ni2+Ni^{2+} (3d83d^8 configuration). Cl−Cl^- is a weak field ligand, so it does not force the two unpaired 3d3d electrons of Ni2+Ni^{2+} to pair up. Nickel uses one 4s4s and three 4p4p orbitals (sp3sp^3 hybridisation, tetrahedral), while the two unpaired 3d3d electrons remain unpaired — so the complex is paramagnetic. In [Ni(CO)4][Ni(CO)_4], nickel is in the zero oxidation state, Ni(0)Ni(0) (3d84s2→3d^84s^2 \to rearranged as 3d104s03d^{10}4s^0 on complex formation). COCO is a very strong field ligand; with all ten 3d3d electrons already paired in this configuration, nickel again uses sp3sp^3 hybridisation (4s,4p4s, 4p orbitals, tetrahedral) but now has no unpaired electrons — so the complex is diamagnetic. Both are tetrahedral (sp3sp^3), but they differ in Ni's oxidation state and hence its d-electron pairing, which is why one is paramagnetic and the other diamagnetic.
  2. [MA2X2] tetrahedral — no geometrical isomerism: In a regular tetrahedron, all four bond positions around the central metal are equivalent — every pair of positions subtends the same bond angle (≈109.5°\approx 109.5°) and every ligand is 'adjacent' (cis) to every other ligand; there is no pair of positions that are 'opposite' (trans) as in square planar or octahedral geometry. Hence only one possible spatial arrangement exists for [MA2X2][MA_2X_2] in a tetrahedral complex, and cis-trans (geometrical) isomerism cannot occur.

OR — VBT for the two coordination entities:

…

Unlock everything free for 14 days

  • Full step-by-step solutions
  • Concept-first explanations
  • Methods, shortcuts & mistakes
  • PYQ mapping + timed mock tests

Full access for 14 days. No credit card required.