Chemistry

Octahedral Tetrahedral And Square Planar Complexes

Coordination complexes are an essential part of inorganic chemistry, playing a crucial role in biological systems, industrial processes, and catalysis. These complexes consist of a central metal ion bonded to ligands in specific geometric arrangements. The most common geometries include octahedral, tetrahedral, and square planar complexes.

Understanding these geometries is vital for predicting reactivity, stability, and magnetic properties. This topic will explore the structures, formation, electronic configuration, and real-world applications of these coordination complexes.

What Are Coordination Complexes?

A coordination complex consists of a metal ion surrounded by ligands (neutral molecules or anions that donate electron pairs to the metal). The arrangement of these ligands determines the geometry of the complex.

Factors Affecting Geometry

Several factors influence the geometry of a coordination complex:
Number of ligands (coordination number)
Electronic configuration of the metal ion
Ligand field strength (Crystal Field Theory and Ligand Field Theory)
Steric effects (size of ligands and metal ion)

Now, let’s examine the three main geometries: octahedral, tetrahedral, and square planar.

1. Octahedral Complexes

Structure of Octahedral Complexes

An octahedral complex has a metal ion surrounded by six ligands arranged at 90° angles, forming an octahedral shape. This is the most common geometry for metal complexes with a coordination number of 6.

Example:

  • [Fe(H₂O)₆]³⁺ (Hexaaquairon(III) ion)
  • [Co(NH₃)₆]³⁺ (Hexaamminecobalt(III) ion)

Electronic Configuration and Crystal Field Splitting

In an octahedral field, the d-orbitals of the metal ion split into two energy levels:
Higher energy level (eg): dx²-y², dz²
Lower energy level (t₂g): dxy, dxz, dyz

The crystal field splitting energy (Δo) determines whether the metal complex follows:

  • High-spin configuration (weak field ligands, small Δo)
  • Low-spin configuration (strong field ligands, large Δo)

Magnetic Properties of Octahedral Complexes

  • High-spin complexes have unpaired electrons, making them paramagnetic (e.g., Fe²⁺, Mn²⁺).
  • Low-spin complexes have paired electrons, making them diamagnetic (e.g., Co³⁺ with strong field ligands).

Examples of Octahedral Complexes in Real Life

  • Hemoglobin (Fe²⁺ complex) transports oxygen in the blood.
  • Transition metal catalysts such as [Cr(NH₃)₆]³⁺ are used in industrial reactions.

2. Tetrahedral Complexes

Structure of Tetrahedral Complexes

A tetrahedral complex consists of a metal ion surrounded by four ligands positioned at 109.5° angles. This geometry occurs when the coordination number is 4, and the ligands are bulky or weak field ligands.

Example:

  • [CuCl₄]²⁻ (Tetrachlorocuprate(II) ion)
  • [Zn(NH₃)₄]²⁺ (Tetraamminezinc(II) ion)

Electronic Configuration and Crystal Field Splitting

In a tetrahedral field, the d-orbitals split into:
Higher energy level (t₂): dxy, dxz, dyz
Lower energy level (e): dx²-y², dz²

Since Δt (tetrahedral splitting energy) is smaller than Δo (octahedral splitting energy), tetrahedral complexes are usually high-spin.

Magnetic Properties of Tetrahedral Complexes

  • Most tetrahedral complexes are paramagnetic due to unpaired electrons.
  • Example: [MnCl₄]²⁻ is paramagnetic with 5 unpaired electrons.

Examples of Tetrahedral Complexes in Real Life

  • Photosynthesis enzymes contain tetrahedral Mn complexes.
  • Catalysts in polymerization involve tetrahedral Ni and Ti complexes.

3. Square Planar Complexes

Structure of Square Planar Complexes

A square planar complex has a metal ion bonded to four ligands, arranged in a square shape (90° angles). This geometry is common for d⁸ metal ions such as Ni²⁺, Pd²⁺, Pt²⁺.

Example:

  • [PtCl₄]²⁻ (Tetrachloroplatinate(II) ion)
  • [Ni(CN)₄]²⁻ (Tetracyanonickelate(II) ion)

Electronic Configuration and Crystal Field Splitting

In a square planar field, the d-orbitals split into four levels:
Highest energy: dx²-y²
Intermediate levels: dxy, dz²
Lowest energy: dxz, dyz

Due to strong ligand fields, square planar complexes are usually low-spin and diamagnetic.

Magnetic Properties of Square Planar Complexes

  • Most square planar complexes are diamagnetic, meaning they have all paired electrons.
  • Example: [PtCl₄]²⁻ is diamagnetic because platinum(II) has a d⁸ configuration.

Examples of Square Planar Complexes in Real Life

  • Cisplatin ([Pt(NH₃)₂Cl₂]), a chemotherapy drug used to treat cancer.
  • Homogeneous catalysts, such as Wilkinson’s catalyst ([RhCl(PPh₃)₃]), used in hydrogenation reactions.

Comparison of Octahedral, Tetrahedral, and Square Planar Complexes

Property Octahedral Complex Tetrahedral Complex Square Planar Complex
Coordination Number 6 4 4
Bond Angles 90° 109.5° 90°
d-Orbital Splitting Large Δo Small Δt Strong ligand field
Spin State High-spin or Low-spin Mostly high-spin Mostly low-spin
Common Metals Fe, Co, Cr, Ni Zn, Cu, Mn Pt, Pd, Ni, Rh
Magnetic Properties Paramagnetic or Diamagnetic Mostly paramagnetic Mostly diamagnetic

Octahedral, tetrahedral, and square planar complexes are the most common geometries in coordination chemistry. Their structure, electronic configuration, and magnetic properties determine their chemical reactivity and industrial applications.

Octahedral complexes (coordination number 6) are highly stable and used in biological and catalytic systems.
Tetrahedral complexes (coordination number 4) are common for d⁰ and d¹⁰ metal ions and often appear in metalloproteins and catalysts.
Square planar complexes (coordination number 4) are preferred by d⁸ metal ions and have applications in medicine and industrial catalysis.

Understanding these geometries allows chemists to design new materials, catalysts, and pharmaceuticals with tailored properties for various applications.