Theoretical models for

the understanding of
complexes
Ligand Field Stabilization
Ligand Field theory

MST - ANO 1
 Models to understand a complex

• Ligand field theory

– Strong ligand field interactions
– Weak ligand field interactions (not to be discussed in ANO)
• MO theory (ANO7A)

MST - ANO 2
 Models are helpful with: **

Interpretation/understanding/prediction of:
• Colors and electronic spectra
• Spin states and magnetic properties
• Preference for certain geometries and distortions
• Effect of π-donating or π-accepting ligands

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 Reflection and absorption

Black: absorbs all colors White: reflects all colors

Yellow: Yellow:
absorbs all colors but yellow; reflects all colors but indigo;
Reflects yellow. Absorbs indigo.

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 Colors of complexes

A solution containing the complex ion [Cu(NH3)4]2+,

is blue because the complex absorbs red and
orange light, the complementary colors of blue and
blue-green.

Why does this complex absorb red and orange light?

MST - ANO 5
 Possible transitions in a complex ***
Lπ*
e

t2 d-d

M MLCT
Lπ

LMCT
Lσ

MLCT = Metal-to-Ligand Charge Transfer

LMCT = Ligand-to-Metal Charge Transfer

NB: Lπ and Lπ* will be explained with MO (ANO7A)

MST - ANO 6
 Intensities of spectroscopic bands
Band type εmax / (dm3 mol–1 cm–1)
example
Spin forbidden <1
[Mn(H2O)6]2+ HS d5
Laporte forbidden, 1 – 100 (e.g. Oh)
spin-allowed “d-d” [Ti(H2O)6]3+ d1
(p-d mixing) 10 – 1000 (e.g. Td)
[NiCl4]2– d8
Symmetry allowed (CT) 1000 – 50.000
[MnO4]–

MST - ANO 7
 Metal orbitals in Oh

MST - ANO 8
 5 d-orbitals of a metal ***

dxy dxz dyz : directed in between axes

t2

e
dx2–y2 dz :
2

directed along axes

MST - ANO 9
 LF transition in a d1 complex

[Ti(H2O)6]3+ d-d transition:

eg eg

t2g t2g

t2g1 eg1

Band at 493 nm
MST - ANO ∆ = 20,300 cm–1 10
 Energies of d orbitals in a complex ***

Splitting d orbitals
Repulsion of metal in Oh ligand field
and ligand electrons

∆ +6 Dq
Energy of
metal d orbitals –4 Dq

∆ = 10 Dq

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 d-orbital splitting in an octahedron ***

Oh = point group
symbol for octahedron
MST - ANO 12
 d-orbital splitting in a tetrahedron ***

Td = point group
symbol for tetrahedron
MST - ANO 13
 d-Orbital splitting ***
• Splitting is 10 Dq (also denoted as Δ)
• Unit is energy, most often cm–1
• The energy difference Δ is dependent on:
– 1) the metal ion and oxidation state;
– 2) the ligand
– 3) the geometry
• For octahedron: ΔO
• For tetrahedron: ΔT

MST - ANO 14
 Comparison Td and Oh splitting ***
dx2–y2 dz2
eg

dxy dxz dyz

t2 +6 Dq
Td +4 Dq ∆ Oh
–6 Dq ∆
–4 Dq
e
t2g
dx2–y2 dz2
dxy dxz dyz

∆T (Td) ≈ 4/9∆O (Oh) for same metal and ligands

• Fewer ligands
• not directly pointing into d orbitals
MST - ANO 15
 Spectrochemical series **

Weak and strong-field ligands

I– < Br– < S2– < SCN– < Cl– < NO2– < N3– < F– <

OH– < C2O42– < H2O < NCS– < CH3CN < py < NH3

< en < bpy < phen < NO2– < Pφ3 < CN– < CO

MST - ANO 16
 Dependence on metal:

Increasing d-orbital splitting for:

Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Co3+ < Mo3+ < Rh3+
< Ru3+ < Pd4+ < Ir3+ < Pt4+
∆O increases with: ***
• Oxidation state of metal ion
– smaller size, larger electrostatic interaction;
shorter metal-ligand distances
• Down a group
– larger size of 4d and 5d orbitals, better overlap;
stronger interactions
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 LF splitting for [M(NH3)6]3+ *

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 [Ni(H2O)6]2+ vs [Ni(NH3)6]2+ *
8900 cm–1; 1125 nm
[Ni(H2O)6]2+

10800 cm–1; 925 nm

[Ni(NH3)6]2+

MST - ANO Visible: 750 – 400 nm 19

 LFSE (CFSE) ***

Ligand (Crystal) Field Stabilization Energy

• The energy by which a complex is stabilized due to
d-orbital splitting.
• LFSE in an octahedron (HS = high-spin) is calculated
by:
LFSE = (# electrons in t2g)(–2/5∆) + (# electrons in eg)(3/5∆)

With ∆ = 10 Dq

For t2gxegy in Oh: LFSE = (0.4x – 0.6y)∆O

MST - ANO 20
 LFSE for octahedral complexes *

LFSE in Dq units for HS dn configuration in Oh

dx2–y2 dz2
d0 0
eg
d1 4 d6 4

d2 8 d7 8
+6 Dq
∆
d3 12 d8 12

d4 6 d9 6 –4 Dq
t2g
d5 0 d10 0 dxy dxz dyz

MST - ANO 21
 LFSE in a graph

d0, d5, d10: no preference for Td or Oh

d3, d8 (LS d6): strong preference for Oh

MST - ANO 22
 Lattice energy for MCl2 *

HS octahedral geometries

MST - ANO 23
 Calculation of LFSE (also for LS) in Oh ***

• Calculation of LFSE can predict whether LS state is

possible
– Calculate the LFSE: for each t2g: –4 Dq, for each eg: +6 Dq
– Calculate pairing energy P in LS state (= additional number of
electron pairs)
• LFSE = (# electrons in t2g)(–4 Dq) + (# electrons in eg)(6 Dq) + nP

• Note: units Dq and P are not the same

• IMPORTANT: Td NEVER LS

MST - ANO 24
 HS and LS for d4 in Oh ***

HS: LS:
CrII in [Cr(H2O)6]Cl2 CrII in K4[Cr(CN)6]
MnIII in [Mn(acac)3] MnIII in K3[Mn(CN)6]

LFSE (HS) = –0.6∆O LFSE (LS) = –1.6∆O + P

MST - ANO 25
 HS and LS for d5 in Oh ***

HS: LS:
MnII in [Mn(H2O)6]2+ MnII in K4[Mn(CN)6]
FeIII in [Fe(H2O)6]3+ FeIII in K3[Fe(CN)6]

LFSE (HS) = 0∆O LFSE (LS) = –2.0∆O + 2P

MST - ANO 26
 HS and LS for d6 in Oh ***

HS: LS:
FeII in [Fe(H2O)6]2+ FeII in K4[Fe(CN)6]

LFSE (HS) = –0.4∆O LFSE (LS) = –2.4∆O + 2P

MST - ANO 27
 HS and LS for d7 in Oh ***

HS: LS:
CoII in [Co(en)2Cl2] CoII in [Co(bpy)3]2+

LFSE (HS) = –0.8∆O LFSE (LS) = –1.8∆O + P

NB: LS Co2+ is easily oxidized!

MST - ANO 28
 LFSE for weak and strong ligands *
dn Oh weak S Oh strong S Extra ↑↓ Td weak
d0 0 0 0 0 0 0
d1 4 Dq(O) ½ 4 Dq(O) ½ 0 6 Dq(T)
d2 8 Dq(O) 1 8 Dq(O) 1 0 12 Dq(T)
d3 12 Dq(O) 1½ 12 Dq(O) 1½ 0 8 Dq(T)
d4 6 Dq(O) 2 16 Dq(O) 1 LS 1 4 Dq(T)
d5 0 2½ 20 Dq(O) ½ LS 2 0
d6 4 Dq(O) 2 24 Dq(O) 0 LS 2 6 Dq(T)
d7 8 Dq(O) 1½ 18 Dq(O) ½ LS 1 12 Dq(T)
d8 12 Dq(O) 1 12 Dq(O) 1 0 8 Dq(T)
d9 6 Dq(O) ½ 6 Dq(O) ½ 0 4 Dq(T)
d10 0 0 0 0 0 0
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 Spin Transitions in Oh Fe(II) species

Left: low spin

Right: high spin
Differences in:
magnetism, optical
properties, ligand
exchange, redox,
electron exchange
MST - ANO 30
 Spin crossover in Fe(II) **

(a) [Fe(phen)2(NCS)2] (b) [Fe(btz)2(NCS)2]

MST - ANO 31
 Distortions in geometries ***

1937: Jahn and Teller:

“a molecule in a degenerate state distorts to lower the
symmetry, remove the degeneracy, and lower the
energy”

Important mostly for d4 and d9 octahedral compounds

Cu(II) = d9
Mn(III) = d4

MST - ANO 32
 Compression vs elongation ***

Compressed octahedron Elongated octahedron

2 short 2 long
4 normal/long 4 normal/short

Octahedron

MST - ANO
6 equal distances 33
 Jahn-Teller distortion for d4 and d9 ***
Axial elongation Axial compression

MST - ANO 34
 HO O
H3C CH3

JT distorted Cu2+ N N

N N

H3C CH3

Cu – Oax = 2.29 Å Cu – Nax = 2.44 Å

Cu – Neq = 2.04 Å Cu – Neq = 2.01 Å
MST - ANO Cu – O = 1.98 Å 35
 Oh  square planar for d8 ***

Strong field ligands

or 4d/5d metals:

∆ = large
 spin pairing

Diamagnetic (no unpaired electrons)

MST - ANO 36
 Crystal field splitting compared ***
1.2

1.0

0.8

0.6

0.4

0.2

–0.2

–0.4

–0.6
SqPl TBP SqPy Oh PentBP SqAntiPr Td
MST - ANO 37
 Summary/keywords

• Ligand field stabilization energy (LFSE) or

Crystal field stabilization energy (CFSE)
• Ligand field splitting; ∆ = 10 Dq;
Oh splitting ∆O ; Td splitting ∆T
• Strong field and weak field ligands;
spectrochemical series
• Jahn-Teller distortion; square-planar geometry
• High spin; low spin; spin pairing energy;
spin crossover

MST - ANO 39
 Assignment

• Study § 20.2 (p 525 – 530)

• Study § 22.1 – 22.5 (p 579 – 587)

MST - ANO 40