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ChemistryMediumClass 12

Isomerism โ€” Geometric, optical, ionization, linkage

Coordination Compounds

15

JEE Qs

8%

Hard

75

min

Practice drawing structures for each type of isomerism for various common complex formulas to develop a systematic approach to identify and count all possible isomers.

๐Ÿงฎ Key Formulas

Geometric Isomerism (Octahedral): MA2B4, MA3B3, M(AA)2B2 (AA=bidentate symmetric ligand) types exhibit cis/trans or fac/mer isomers.
Geometric Isomerism (Square Planar): MA2B2, MABCD types exhibit cis/trans isomers. Tetrahedral complexes rarely show geometric isomerism.
Optical Isomerism: A complex is optically active (chiral) if it is non-superimposable on its mirror image, which implies the absence of a plane of symmetry and a center of symmetry. Common chiral types: M(AA)3, cis-M(AA)2B2, M(AA)(BB)(CC), etc.
Linkage Isomerism: Requires an ambidentate ligand, which can bind to the central metal atom through two different donor atoms (e.g., NO2- (nitro/nitrito), SCN- (thiocyanato/isothiocyanato), CN- (cyano/isocyano)).
Ionization Isomerism: Involves the exchange of an ion inside the coordination sphere with an ion outside the coordination sphere (counter-ion). The isomers yield different ions in solution.

โœ… Key Points for JEE

  • 1Systematically draw all possible structural arrangements for a given complex before determining isomer types. Rotation of the entire molecule or specific ligands should not be counted as new isomers.
  • 2For geometric isomerism, focus on the relative positions of identical ligands. Square planar (e.g., MA2B2) and octahedral (e.g., MA2B4, MA3B3) complexes are key; tetrahedral complexes generally do not show geometric isomerism.
  • 3For optical isomerism, determine if a complex is chiral by checking for the presence of a plane of symmetry or a center of symmetry. If either is present, the complex is generally achiral. Cis isomers of bidentate chelates (e.g., cis-[M(AA)2B2]) are often optically active.
  • 4Identify ambidentate ligands (e.g., NO2-, SCN-, CN-) as a prerequisite for linkage isomerism. Different bonding modes lead to distinct isomers with different properties.
  • 5Ionization isomerism requires interchangeable ligands and counter-ions. Check if exchanging an inner-sphere ligand with an outer-sphere counter-ion results in a different complex formula and different ions in solution.

โš ๏ธ Common Mistakes

  • โœ•Failing to identify a plane of symmetry or a center of symmetry, leading to incorrect assessment of optical activity.
  • โœ•Confusing geometric isomers with optical isomers, or double-counting structures that are identical through rotation.
  • โœ•Missing potential isomers by not considering all possible ligand arrangements or not recognizing ambidentate ligands.
  • โœ•Incorrectly applying the rules for different coordination numbers and geometries (e.g., assuming tetrahedral complexes show geometric isomerism).

๐Ÿ“ Practice Questions

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Q74.In the Claisen-Schmidt reaction to prepare, dibenzalacetone from 5.3 g of benzaldehyde, a total of 3.51 g of product was obtained. The percentage yield in this reaction was ______ %.

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Q61.The calculated spin-only magnetic moments of K3 [Fe(OH)6] and K4 [Fe(OH)6] respectively are : (1) 3.87 and 4.90 B.M. (2) 4.90 and 5.92 B.M. (3) 4.90 and 4.90 B.M. (4) 5.92 and 4.90 B.M.

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Q54.Identify the homoleptic complexes with odd number of d electrons in the central metal : (A) [FeO4]2โˆ’ (B) [Fe(CN)6]3โˆ’ (C) [Fe(CN)5NO]2โˆ’ (D) [CoCl4]2โˆ’ (E) [Co(H2O)3 F3] Choose the correct answer from the options given below : (1) (A), (B) and (D) only (2) (C) and (E) only (3) (B) and (D) only (4) (A), (C) and (E) only

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Q68.In which of the following complexes the CFSE, ฮ”o will be equal to zero? (1) [Fe(en)3]Cl3 (2) K4 [Fe(CN)6] (3) [Fe(NH3)6]Br2 (4) K3 [Fe(SCN)6]

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Q70.From the magnetic behaviour of [NiCl4]2โˆ’ (paramagnetic) and [Ni(CO)4] (diamagnetic), choose the correct geometry and oxidation state. (1) [NiCl4]2โˆ’: NiII , tetrahedral [Ni(CO)4] : NiII , (2) [NiCl4]2โˆ’ : NiII , square planar [Ni(CO)4] : Ni(0) square planar , square planar (3) [NiCl4]2โˆ’: NiII , tetrahedral [Ni(CO)4] : Ni(0), (4) [NiCl4]2โˆ’: Ni(0), tetrahedral [Ni(CO)4] : Ni(0), tetrahedral square planar

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Q53.The correct order of the following complexes in terms of their crystal field stabilization energies is : (1) [Co(NH3)4]2+ < [Co(NH3)6]2+ < [Co(en)3]3+ < [Co(NH3)6]3+ (2) [Co(NH3)6]2+ < [Co(NH3)6]3+ < [Co(NH3)4]2+ < [Co(en)3]3+ (3) [Co(en)3]3+ < [Co(NH3)6]3+ < [Co(NH3)6]2+ < [Co(NH3)4]2+ (4) [Co(NH3)4]2+ < [Co(NH3)6]2+ < [Co(NH3)6]3+ < [Co(en)3]3+

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NCERT Chapters

  • Class 12 Chemistry Ch 9: Coordination Compounds