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Coordination Compounds - Isomerism in Coordination Compounds

Grade 12CBSEChemistry

Review the key concepts, formulae, and examples before starting your quiz.

🔑Concepts

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Isomerism in coordination compounds describes molecules with the same chemical formula but different structural arrangements or spatial orientations. It is broadly classified into Structural Isomerism and Stereoisomerism.

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Structural Isomerism includes: 1. Linkage Isomerism (arises with ambidentate ligands like NO2−NO_2^- or SCN−SCN^-); 2. Ionization Isomerism (interchange of ions between the coordination sphere and the ionization sphere); 3. Coordination Isomerism (interchange of ligands between cationic and anionic entities); 4. Solvate Isomerism (differing number of H2OH_2O molecules inside the coordination sphere).

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Stereoisomerism includes: 1. Geometrical Isomerism (cis/transcis/trans and fac/merfac/mer); 2. Optical Isomerism (chiral molecules that are non-superimposable mirror images).

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Geometrical Isomerism: In square planar complexes of type [MA2B2][MA_2B_2], ciscis (adjacent) and transtrans (opposite) forms exist. In octahedral complexes of type [MA3B3][MA_3B_3], isomers are designated as facfac (facial) and mermer (meridional).

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Optical Isomerism: Common in octahedral complexes containing chelating didentate ligands such as ethylenediamine (enen). Enantiomers are labeled as dd (dextro) and ll (laevo) based on their rotation of plane-polarized light.

📐Formulae

Square Planar: [MA2B2]→cis,trans\text{Square Planar: } [MA_2B_2] \rightarrow cis, trans

Octahedral: [MA4B2]→cis,trans\text{Octahedral: } [MA_4B_2] \rightarrow cis, trans

Octahedral: [MA3B3]→fac,mer\text{Octahedral: } [MA_3B_3] \rightarrow fac, mer

Optical Activity: [M(en)3]n+→d and l forms\text{Optical Activity: } [M(en)_3]^{n+} \rightarrow d \text{ and } l \text{ forms}

💡Examples

Problem 1:

Identify the type of isomerism exhibited by the pair [Co(NH3)5(SO4)]Br[Co(NH_3)_5(SO_4)]Br and [Co(NH3)5Br]SO4[Co(NH_3)_5Br]SO_4.

Solution:

Ionization Isomerism.

Explanation:

These isomers yield different ions in solution. [Co(NH3)5(SO4)]Br[Co(NH_3)_5(SO_4)]Br gives Br−Br^- ions, whereas [Co(NH3)5Br]SO4[Co(NH_3)_5Br]SO_4 gives SO42−SO_4^{2-} ions.

Problem 2:

How many geometrical isomers are possible for the square planar complex [Pt(NH3)(NH2OH)(Py)(Cl)]+[Pt(NH_3)(NH_2OH)(Py)(Cl)]^+?

Solution:

33 geometrical isomers.

Explanation:

For a square planar complex of type [MABCD][MABCD], three isomers are possible by fixing one ligand and rotating the other three.

Problem 3:

Explain why [Co(en)3]3+[Co(en)_3]^{3+} shows optical isomerism while trans−[Co(NH3)4Cl2]+trans-[Co(NH_3)_4Cl_2]^+ does not.

Solution:

[Co(en)3]3+[Co(en)_3]^{3+} is chiral, whereas trans−[Co(NH3)4Cl2]+trans-[Co(NH_3)_4Cl_2]^+ has a plane of symmetry.

Explanation:

Optical isomerism requires the absence of a plane of symmetry. In [Co(en)3]3+[Co(en)_3]^{3+}, the didentate ligands create a helical, non-superimposable structure. The transtrans-isomer of [Co(NH3)4Cl2]+[Co(NH_3)_4Cl_2]^+ is achiral due to its symmetrical arrangement.