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• Ligand Field Thoery (aka Crystal Field Theory) assumes that the only
interaction between the metal and the ligands is purely ionic.
• Imagine the five d-orbitals in an isolated metal ion; energetically degenerate.
─ ─ ─ ─ ─
spherical field
M E M
─ ─ ─ ─ ─
no ligand field
• Under these conditions, which d-orbitals will interact most strongly with the
ligands? dx2-y2 and dz2.
• These two orbitals (designated eg) will increase in energy to the same extent.
The remaining orbitals (designated t2g) will also be repelled by the incoming
ligands, but to a much lesser extent.
• The difference in energy between the eg and t2g orbitals is defined as “10Dq”.
• Relative to a barycenter of the spherical field, the eg orbitals are seen as being
repelled by 6Dq, while the t2g orbitals are stabilized by 4Dq.
Ligand Field Stabilization Energy (LFSE)
• What happened when 1 electron is added to the Oh ligand field?
– it goes in a t2g orbital and, therefore, d1 (t2g1eg0) has an LFSE of -4Dq. ─ ─
─ ─ ─
• A second electron will also go into a t2g orbital (won’t pair).
– thus, d2 (t2g2eg0) has an LFSE of -8Dq. ─ ─
─ ─ ─
• A third electron will also go into a t2g orbital.
– thus, d2 (t2g3eg0) has an LFSE of -12Dq.
─ ─
─ ─ ─
• Note now that the t2g orbitals are half filled. If we add a fourth electron
there are two places it can go.
─ ─ ─ ─
─ ─ ─ ─ ─ ─
─ ─
– hs d9(t2g6eg3) has an LFSE of (6 x -4Dq) + (3 x 6Dq) = -6Dq.
─ ─ ─
─ ─ ─
S = (2 x ½) = 1
─ ─
– ls d5(t2g5eg0)
has an LFSE of (5 x -4Dq) + 2P = -20Dq + 2P.
S = (1 x ½) = 1/2 ─ ─ ─
– Pairing energies based on change in pairing on going from hs to ls and are NOT
calculated from absolute number of pairs.
─ ─
– ls d6(t2g6eg0)
has an LFSE of (6 x -4Dq) + 2P = -24Dq + 2P.
S = (0 x ½) = 0 ─ ─ ─
A Comparison of the Weak Field and Strong Field Cases
─ ─
─ ─
─ ─ ─ ─ ─ ─
10Dq < P 10Dq > P
high spin case low spin case
Evidence for Ligand Field Stabilization Energy
• First evidence that LFSE might be important in
transition metal complexes came from an
examination of lattice energies (E α 1/r).
– Since ionic radii decrease gradually across 1st
transition row, would expect gradual increase in
energy.
– However, curve is not smooth and only Ca+2, Mn+2
and Zn+2 fall on theoretical straight line.
– What can you say about the LFSE of these 3 ions
(assume high spin case)? d0 d5 d10 LFSE for
these? = 0
– Why are the other ions above this line?
= 239 KJ/mole
Factors Affecting Pairing Energies and 10Dq.
– Pairing energies tend to fall in a fairly narrow range (~230 – 280 KJ/mole).
Factors Affecting Pairing Energies and 10Dq
2. 10Dq affected by:
a. Oxidation state of the metal; as the oxidation number increases, so does 10Dq. Can
justify this in terms of the ligand field model. The increased positive
charge on the metal will bring the ligands in towards it, thus destabilizing
the eg orbitals.
Factors Affecting Pairing Energies and 10Dq
2. 10Dq affected by:
b. Number and geometry of the ligands; the splitting in Oh field ~9/4 times that in Td
field. Due to 1/3 fewer ligands in Td case (will decrease the field by
33.3%) and the fact that the ligands are not overlapping with orbitals as
much as in the Oh case.
Factors Affecting Pairing Energies and 10Dq
2. 10Dq affected by:
c. Nature of the ligands. Table 16.2 shows 10Dq’s for
various Cr(III) complexes. Note that as the ligands
change, so does 10Dq. Table 9.7 shows 10Dq values
for a number of metals with a number of ligands.
Notice that although the absolute values of the 10Dq’s
are different, the trend of the effect that a ligand has
on a metal ion is the same from metal to metal.
Cr(III): Cl- < dtp < F- < H2O < NH3 < en < CN
Rh(III): Cl- < dtp < H2O < NH3 < en < CN
• C.K. Jørgensen (no relation) has attempted to predict values of 10Dq based
on the spectrochemical series and various metals.
10Dq = fligand x gion x 103 cm-1 e.g. [CrCl6]-3
10Dq = fligand x gion x 103
= (0.78) x (17.4) x 103
= 13,572 cm-1 (736 nm)
z-out Oh z-in
Square Planar Coordination
• If we start with Oh coordination and then introduce tetragonal distortion (z-out) until
those ligands along the z-axis are removed to infinity, a square planar coordination is
achieved.
Oh Sq Pl
• Metal ions which have a d8 configuration and ligands high in the spectrochemical series
(low spin) favor square planar coordination. For example, [Ni(CN)4]-2 , [PdCl4]-2 and
[Pt(NH3)4]+2 are all d8 square planar complexes.
• Why only low spin square planar complexes?
• The weak field/high spin case doesn’t result in any stabilization, whereas the low spin
situation does result in stabilization. ─ ─
• Note: xy → x2-y2 = 10Dq. ─ ─
─ ─
─ ─ ─ ─
Tetrahedral Coordination
• Again, imagine the set of five d-orbitals in spherical
symmetry. Next imagine eight ligands approaching the
central metal from along the corners of a cube.
• In this case the ligands don’t approach directly any
of the d-orbitals, but do come closest to the t2g
orbitals, thus destabilizing them. This would
represent cubic symmetry.
• The energy level diagram for tetrahedral symmetry is
qualitatively similar to cubic symmetry, but 10Dq is
only half as large.
• Because tetrahedral systems have no center of
symmetry, can’t have t2g and eg, just t2 and e.
• Because 10Dq for tetrahedral complexes is 4/9 of
the octahedral case, only weak field (high spin)
species are observed.
Molecular Orbital Theory
• Although LFT is useful and can be used to account for a large number
of observations, it does have its drawbacks.
1. It assumes that both metal and ligands are point charges (with no volume).
2. It assumes that all bonding is strictly ionic.
– Anomoly: the ligand with the strongest field is CO, which has no ionic
charge.
• Is there covalent bonding?
– Indirect evidence: electron-electron repulsions in metal complexes are
somewhat less than in free ions. This may be due to the formation of
molecular orbitals, which are larger than atomic orbitals and would reduce
repulsions. This is known as the nephelauxetic effect (cloud expanding).
– Direct evidence: in electron spin resonance (esr) unpaired electrons can align
parallel or antiparallel to an applied magnetic field and we can get a
transition by applying radiation (like nmr). An isolated metal ion shows a
“singlet”. However, many complexes show a more complicated spectra
indicating that the electron is spending some of its time “away” from the
metal. That is, it is behaving covalently.
Comparison of LFT and MOT Approaches to Bonding
• Consider a simple system: a Lewis base (B) having one
orbital with an electron pair to be donated, and a Lewis
acid (A+), with two sp orbitals available for bonding and
a single odd electron.
B : + A ● + → [AB]+
A1 A2
B : + A ● + → [AB]+
A1 A2
t1u
——
4p ——
• Assume that the compound [Co(NH3)6]+2 ——
has pure Oh symmetry.
a1g
• From the Oh Character Table, determine 4s ——
the irreducible representations to which the
3d, 4s and 4p orbitals of cobalt belong.
eg + t2g
• Next, use the σ-bonds as a basis to find the ——
3d ——
——
—— a1g + eg + t1u
reducible representation for the ligands. ——
—— ——
——
——
——
—— 6L
——
Oh E 8C3 6C2 6C4 3C2’ i 6S4 8S6 3σh 6σd
Γ 6 0 0 2 2 0 0 0 4 2
3. Molecular orbitals.
– π* orbitals of polyatomic ligands.
– e.g. CO, CN, pyridine.
Pi-Bonding in the Octahedral Case.
• This reduces to: t1u + t2u + t2g + t1g. Only the t2g can
overlap with the metal ion.
• Case 1: empty π-orbitals on ligand that are higher in energy
than the metal t2g orbitals (e.g. phosphenes, CO, CN).
– in this case π-bonding increases 10Dq.
• Case 2: ligand has filled π-bonding orbitals which are lower
in energy than metal t2g orbitals (e.g. F-, O2-).
– in this case π-bonding decreases 10Dq.