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Revision: Coordination Compounds CUET (UG) Coordination Compounds

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Definitions [9]

Definition: Isomerism

Isomerism is the phenomenon in which compounds have the same molecular formula but differ in their physical or chemical properties due to a different arrangement of atoms or groups in space or structure.

Define the term Hydrated isomers.

Isomers in which there is exchange of solvent (water) ligands between coordination and ionization spheres are called hydrate isomers.

Define Distereoisomers.

Two or more coordination compounds which contain the same number and types of atoms, and bonds (i.e., the connectivity between atoms is the same), but which have different spatial arrangements of the atoms are called distereoisomers.

Define the term Co-ordination isomer.

Isomers which show interchange of ligands between cationic and anionic spheres of different metal ions are called co-ordination isomers.

Define the term Hydrated isomers.

Isomers in which there is exchange of solvent (water) ligands between coordination and ionization spheres are called hydrate isomers.

Definition: Isomerism

Isomerism is the phenomenon in which compounds have the same molecular formula but differ in their physical or chemical properties due to a different arrangement of atoms or groups in space or structure.

Define Distereoisomers.

Two or more coordination compounds which contain the same number and types of atoms, and bonds (i.e., the connectivity between atoms is the same), but which have different spatial arrangements of the atoms are called distereoisomers.

Define the term Co-ordination isomer.

Isomers which show interchange of ligands between cationic and anionic spheres of different metal ions are called co-ordination isomers.

Define the following term:

Anomers 

Anomers are stereoisomers of sugars that differ only in the configuration of the hydroxyl group at the C1 position. They are not mirror images of each other.

Key Points

Key Points: Isomerism in Coordination Compounds
Main Type Subtype Description Example
Stereoisomerism Geometrical isomerism Different spatial arrangement (cis–trans) [Pt(NH₃)₂Cl₂]
  Optical isomerism Non-superimposable mirror images [Co(en)₃]³⁺
Structural isomerism Ionisation isomerism Exchange of ions inside/outside the coordination sphere [Co(NH₃)₅SO₄]Br and [Co(NH₃)₅Br]SO₄
  Linkage isomerism Ligand attaches through different donor atoms [Co(NH₃)₅NO₂]Cl₂ and [Co(NH₃)₅ONO]Cl₂
  Coordination isomerism Exchange of ligands between complex ions [Co(NH₃)₆][Cr(CN)₆] and [Co(CN)₆][Cr(NH₃)₆]
  Solvate isomerism Exchange of solvent molecules [Cr(H₂O)₆]Cl₃ and [Cr(H₂O)₅Cl]Cl₂·H₂O
Key Points: Isomerism in Coordination Compounds
Main Type Subtype Description Example
Stereoisomerism Geometrical isomerism Different spatial arrangement (cis–trans) [Pt(NH₃)₂Cl₂]
  Optical isomerism Non-superimposable mirror images [Co(en)₃]³⁺
Structural isomerism Ionisation isomerism Exchange of ions inside/outside the coordination sphere [Co(NH₃)₅SO₄]Br and [Co(NH₃)₅Br]SO₄
  Linkage isomerism Ligand attaches through different donor atoms [Co(NH₃)₅NO₂]Cl₂ and [Co(NH₃)₅ONO]Cl₂
  Coordination isomerism Exchange of ligands between complex ions [Co(NH₃)₆][Cr(CN)₆] and [Co(CN)₆][Cr(NH₃)₆]
  Solvate isomerism Exchange of solvent molecules [Cr(H₂O)₆]Cl₃ and [Cr(H₂O)₅Cl]Cl₂·H₂O
Key Points: Valence Bond Theory (VBT)
  • Proposed by Heitler and London (1927), further developed by Pauling and Slater.
  • A covalent bond is formed when half-filled valence atomic orbitals of similar energies overlap, each containing one unpaired electron.
  • Greater the overlap → stronger the bond.

Types of Orbital Overlap:

Type Description Bond Formed
Axial (Head-on) overlap Orbitals overlap along the internuclear axis Sigma (σ) bond
Sidewise (Lateral) overlap Orbitals overlap parallel to each other, perpendicular to the internuclear axis Pi (π) bond

Hybridisation & Shapes:

Hybridisation Shape Coordination No.
sp³ Tetrahedral 4
dsp² Square planar 4
sp³d Trigonal bipyramidal 5
d²sp³ Octahedral (inner) 6
sp³d² Octahedral (outer) 6
Key Points: Crystal Field Theory (CFT)
  • d-orbitals of metal ion split into lower and higher energy levels in the presence of ligands
  • In a free ion, d-orbitals are degenerate (same energy)
  • Spectrochemical Series

I⁻ < Br⁻ < Cl⁻ < S²⁻ < F⁻ < OH⁻ < C₂O₄²⁻ < H₂O < NCS⁻ < EDTA < NH₃ < en < CN⁻ < CO

Key Points: Colour in Coordination Compounds
  • d-orbitals split into t₂g (low) and eg (high) energy levels
  • The energy difference lies in the visible region
  • Electron jumps from t₂g to eg energy level, which is called d–d transition.
  • d¹ to d⁹ ions → coloured
  • d⁰ and d¹⁰ ions → colourless
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