Chemistry

Coordination compounds

Ligands, coordination number, crystal field, colour, and an 18-electron sketch.

Basics

Metal and ligands

A coordination compound is a Lewis-acid metal ion bound to Lewis-base ligands. Coordination number is how many atoms attach directly (often 4 or 6). Monodentate ligands occupy one site; chelates (en, EDTA) occupy several and often gain stability (the chelate effect). Charge balance and oxidation number keep the formula honest. IUPAC names exist; in class, first count the ligands and the metal.

Geometry and isomers

Four-coordinate complexes are tetrahedral or square planar; six-coordinate ones are usually octahedral. The same formula can hide linkage isomers (SCN⁻ vs NCS⁻), ionisation isomers, and optical isomers of chiral chelates. Cis–trans shows up in octahedral Ma₄b₂ and square-planar Ma₂b₂. Stereochemistry changes catalysis, colour, and magnetism. Draw wedges and dashes for front and back.

Crystal field and colour

Ligands split the d set by a gap Δ. In octahedral geometry t₂g lies below e_g. A large Δ favours pairing (low spin); a small Δ favours high spin. The colour you see is the complement of the absorbed gap. The spectrochemical series (I⁻ < … < CN⁻) ranks how much a ligand raises Δ. Magnetism tracks unpaired electrons.

18-electron sketch

In organometallic chemistry, counting the metal valence electrons plus those donated by ligands often lands near 18 (a krypton-like shell). Exceptions are common; catalytic cycles may swing 16–18. Ni(CO)₄ and Fe(CO)₅ are textbook cases. Pick one counting convention (ionic vs covalent) per problem. Toxic carbonyls have their own lab rules.

Formulas

Complex charge

q_complex = ox_metal + Σ q_ligand

Sum the metal oxidation number and ligand charges.

Symbols

  • ox_metal metal oxidation number
  • q_ligand charge of each ligand

Octahedral crystal-field split

Δ_o = E(e_g) − E(t₂g)

If absorption sits near this energy, a colour appears.

Symbols

  • Δ_o octahedral splitting

Crystal-field stabilisation (octahedral)

CFSE = (−0.4 n_{t₂g} + 0.6 n_{e_g}) Δ_o + n_p P

Occupancy plus pairing energy P. Sign conventions vary slightly by text.

Symbols

  • n_{t₂g} electrons in t₂g
  • P pairing energy

Key table

Haemoglobin Fe coordination; O₂ binding changes colour and shape — a bio-complex
Square planar common for d⁸ (Ni²⁺, Pd²⁺, Pt²⁺)
Strong-field ligands CN⁻, CO, en — large Δ, low-spin tendency

In this field