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Coordination Chemistry Overview

Jun 6, 2025

Overview

This lecture covers the fundamentals of coordination compounds, including their types, key terminology, theories of bonding, isomerism, preparation, identification, and organometallic chemistry.

Introduction to Coordination Compounds

  • Coordination compounds form due to transition metals' tendency for complex formation.
  • Addition compounds are classified as double salts (unstable in solution) and coordination/complex compounds (retain identity in solution).
  • Double salts dissociate into constituent ions in water, while complex compounds do not.

Types of Coordination Compounds

  • Classified based on cation/anion complexity: simple cation/complex anion, complex cation/simple anion, both complex, or neutral.
  • Based on stability: perfect complexes (highly stable), imperfect complexes (less stable).

Key Terminologies

  • Central metal atom/ion accepts electron pairs from ligands to form coordinate bonds.
  • Ligands are electron pair donors (Lewis bases) and can be anionic, neutral, or cationic, and mono- to hexadentate.
  • Chelating ligands form rings with the metal, increasing complex stability.
  • Coordination number: number of donor atoms bonded to metal.
  • Coordination sphere includes the central metal and attached ligands (in square brackets).
  • Oxidation number: effective charge on metal after ligand removal; found by charge balance.
  • Effective Atomic Number (EAN): atomic number adjusted for electrons lost/gained in complex formation.

Formula and Nomenclature

  • Cation is written before anion; complex part in brackets.
  • Ligands listed in alphabetical order before metal in IUPAC names; anionic ligands end with -o, and special names are given to some neutral ligands.
  • Prefixes indicate number of each ligand; bis/tris/tetrakis used for ligands with internal numerical prefixes.
  • Metal is named based on charge and whether the complex is cationic, anionic, or neutral.

Isomerism in Coordination Compounds

  • Structural isomerism: different connectivity (ionization, hydrate, linkage, polymerization, coordination, and position isomerism).
  • Stereoisomerism: same bonds, different spatial arrangement (geometrical and optical isomerism).
  • Geometrical isomers: cis (adjacent ligands) and trans (opposite ligands) forms.
  • Optical isomers: non-superimposable mirror images (dextro, laevo forms).

Preparation and Identification

  • Complexes prepared by substitution, combination, or redox reactions.
  • Identified by changes in solubility, conductivity, chemical properties, color, pH, EMF, or magnetic properties.

Theories of Bonding

  • Werner's theory distinguishes primary (ionizable) and secondary (coordination number) valencies.
  • Valence Bond Theory: metal orbitals hybridize to accommodate ligand electron pairs; predicts geometry and magnetism.
  • Crystal Field Splitting Theory: ligand field splits d-orbital energies, explaining color, magnetism, and stability.
  • Spectrochemical series ranks ligands by their field strength.

Organometallic Compounds

  • Compounds with metal–carbon bonds, classified as covalent or ionic.
  • Sigma- and pi-bonded complexes, including metal carbonyls and sandwich compounds (e.g., ferrocene).
  • Bonding involves both σ-donation and π-backbonding.
  • Synthesized by direct combination, alkylating agents, or reactions yielding Grignard reagents.

Key Terms & Definitions

  • Coordination compound — Compound with a central metal atom/ion bonded to ligands.
  • Ligand — Ion/molecule donating electron pairs to a metal.
  • Chelation — Binding of a metal ion by a polydentate ligand forming a ring.
  • Coordination number — Number of ligand donor atoms attached to the metal.
  • Isomerism — Same formula, different structures or spatial arrangements.
  • Spectrochemical series — Ranking of ligands by crystal field splitting strength.
  • Crystal Field Splitting — Separation of d-orbital energies in a ligand field.

Action Items / Next Steps

  • Review and practice IUPAC nomenclature for given complexes.
  • Solve problems related to isomerism and bonding theories.
  • Prepare for upcoming homework or quizzes on coordination chemistry concepts.