Crystal Field Theory of Coordination Complexes

• historically developed for solid state crystal lattices

• adapted for molecular complexes (later versions: ligand field theory)
• purely ionic model, ligands treated as point charges
• M-L interaction limited to electrostatic repulsion and splitting of M d-orbitals
• can explain spectroscopy, magnetism, and reactivity trends of d-block compounds

Field Splitting of Orbitals

•
n+ • pointing at ligands:
• Mn+ •
n+ n+
M M
M destabilized relative to spherical field
•
•
E "eg"

"t2g"

6 localized pointing between ligands:

free spherical point charges: stabilized relative to spherical field
metal ion charge field octahedral
field

Octahedral Splitting and Crystal Field Stabilization Energy

low spin high spin

(strong field) (weak field) eg
– dz2 dx2–y2
#e config CFSE config CFSE
1 1 0 + 6Dq
d t2g eg –4Dq
d2 t2g2eg0 –8Dq Octahedral Field
d3 t2g3eg0 –12Dq
d4 t2g4eg0 –16Dq t2g3eg1 –6Dq 10Dq = Δoct
d5 t2g5eg0 –20Dq t2g3eg2 0Dq
d6 t2g6eg0 –24Dq t2g4eg2 –4Dq
d7 t2g6eg1 –18Dq t2g5eg2 –8Dq
d8 t2g6eg2 –12Dq – 4Dq
dxy dxz dyz
d9 t2g6eg3 –6Dq t2g
d10 t2g6eg4 0Dq

Licensed by WSM under a Creative Commons Attribution‐NonCommercial‐ShareAlike 2.5 Canada Licence. 
Tetrahedral Splitting Factors that Affect ∆
An alternate view of a tetrahedron: a cube with half the corners missing 1) Number of ligands and geometry (see previous)

Three orbitals point at ligands 2) Oxidation state: ∆↑ as n+ ↑ (Note: n is oxidation state, not principal QN)
• • z
y MLn ∆o (cm )
–1
MLn ∆o (cm )
–1

[Cr(H2O)6]2+ 14100 [Fe(H2O)6]2+ 9400

• • x [Cr(H2O)6]3+ 17400 [Fe(H2O)6]3+ 13700
dxz dyz dxy
"t2"
Two orbitals point between ligands dxy dxz dyz 3) Period: ∆↑ down a column
• • Tetrahedral Field + 1.78Dq
–1
MLn ∆o (cm )
• • [Co(NH3)6] 3+
22900
[Rh(NH3)6]3+ 24000
• • [Ir(NH3)6]3+ 41200
4.45Dq = ∆tet
• • • • y
x
dz2 4) Ligands: Spectrochemical Series
• •
– 2.67Dq MLn ∆o (cm )
–1
MLn
–1
∆o (cm ) MLn ∆o (cm )
–1
dz2 dx2–y2
dx2–y2
[CrF6]3– 15000 [CoF6]3–
13100 [FeCl6]3– 11000
"e"
[Cr(H2O)6]3+ 17500 [Co(H2O)6]3+ 18200 [Fe(H2O)6]3+ 13700
∆tet splitting is inverse of ∆oct: two below three rather than three below two
[Cr(NH3)6]3+ 21500 [Co(NH3)6]3+ 22900 [Fe(NH3)6]3+ 17500
∆tet splitting ≈ ½∆oct: tetrahedral compounds are almost always HS
[Cr(CN)6]3– 26700 [Co(CN)6]3+ 33500 [Fe(CN)6]3– 32800

Crystal Field Splitting for Common Geometries (Dq units) Spectrochemical Series: Ligand Effect on ∆
I– < Br– < Cl– < ONO– < F– < OH– < H2O < MeCN < py < NH3 < en < bpy < phen < NO2– < PR3 < CN– < CO
dx2–y2 ←→
+12.28
dz2 weaker field, smaller splitting stronger field, larger splitting
+10.28

dz2
dz2 dx2–y2 +7.07 Some rules of thumb about the magnitude of ∆:
+6.00 • Tetrahedral complexes tend to be high spin
E • Octahedral complexes will be high spin only if
dxy
dxy dxz dyz
+2.28 dxz dyz • first row transition metal (3d), AND
+1.78
+1.14 • either weak field ligand or low oxidation state
0 Dq
–0.82
dxy dx2–y2
–2.67 –2.72
dz2 dx2–y2 dz2 dxz dyz An aside:
–4.00 –4.28
dxy dxz dyz
–5.14 cm–1 = wavenumbers, a unit of energy favoured by certain breeds of spectroscopist
dxz dyz –6.28   
dxy dx2–y2 ν = = so E = hν =  1000 cm–1 ≈ 12 kJ/mol
= hcν
octahedral tetrahedral square trigonal   
planar linear bipyramidal

Licensed by WSM under a Creative Commons Attribution-NonCommercial-ShareAlike 2.5 Canada Licence. Licensed by WSM under a Creative Commons Attribution-NonCommercial-ShareAlike 2.5 Canada Licence.