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Advanced Chemistry — Coordination Chemistry

Transition metal complexes, bonding, and crystal field theory

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ligand_field_lf 21 terms Feb 9, 2026
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Terms 21

1
Coordination Complex
Central metal ion surrounded by coordinating ligands; [Co(NH₃)₆]³⁺
2
Ligand
Lewis base donating electron pair to metal; monodentate (one donor) or polydentate (chelate)
3
Chelate Effect
Polydentate ligands bind more strongly than equivalent monodentate; entropic advantage
4
Coordination Number
Number of donor atoms bound to central metal; typically 4 or 6
5
Geometry of Complexes
CN=6: octahedral; CN=4: tetrahedral or square planar; CN=2: linear
6
Crystal Field Theory (CFT)
Electrostatic model; ligands split d-orbital energies; explains color and magnetism
7
Crystal Field Splitting (Δ)
Energy difference between d-orbital sets; Δ_o (octahedral) > Δ_t (tetrahedral)
8
t₂g and eg Orbitals
Octahedral: t₂g (lower, 3 orbitals) and eg (upper, 2 orbitals); splitting by ligand field
9
High-Spin vs Low-Spin
Depends on Δ vs pairing energy; strong field ligands → low-spin; weak field → high-spin
10
Spectrochemical Series
Ordering of ligands by field strength: I⁻ < Br⁻ < Cl⁻ < F⁻ < OH⁻ < H₂O < NH₃ < en < CN⁻ < CO
11
Color of Complexes
Complementary color of absorbed light; [Ti(H₂O)₆]³⁺ absorbs green, appears purple
12
Jahn-Teller Distortion
Asymmetric d-electron occupation causes geometric distortion; common in Cu²⁺ (d⁹) octahedral
13
Ligand Field Stabilization Energy (LFSE)
Extra stability from preferential d-orbital filling; low-spin complexes more stable
14
Trans Influence
Strong trans-directing ligand weakens bond to ligand opposite it; thermodynamic
15
Cis vs Trans Isomers
Geometric isomers in square planar and octahedral complexes; different properties
16
Optical Isomers (Δ and Λ)
Non-superimposable mirror images in octahedral tris-chelate complexes
17
18-Electron Rule
Stable organometallic complexes have 18 valence electrons; analogous to octet rule
18
π-Backbonding
Metal donates d-electron density into empty ligand π* orbital; stabilizes CO, CN⁻ complexes
19
Oxidative Addition
Substrate inserts into metal-X bond; metal oxidation state increases by 2; key step in catalysis
20
Reductive Elimination
Two ligands couple and leave metal; metal oxidation state decreases by 2; reverse of oxidative addition
21
Migratory Insertion
Ligand migrates and inserts into metal-ligand bond; key step in polymerization, hydroformylation