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It was not until 1927, however, that Walter Heitler and Fritz
London showed how the sharing of pairs of electrons holds a
covalent molecule together.
The last major step in the evolution of this theory was the suggestion
by Linus Pauling that atomic orbitals mix to form hybrid orbitals,
such as the sp, sp2, sp3, dsp3, and d2sp3 orbitals.
The Valence-Bond Theory
Note: Such a situation will not arise for for d1, d2 and d3 ion configuration.
Deficiencies of VB approach to bonding
Let's assume that the six O2- ions that surround each Mn2+ ion
define an XYZ coordinate system. Two of the 3d orbitals (dx2-y2 and
dz2) on the Mn2+ ion point directly toward the six O2- ions. The other
three orbitals (dxy, dxz, and dyz) lie between the O2- ions.
• d orbitals (dxy, dxz and dyx) with lobes in-between the ligands
experience less repulsion Î placed at lower energy t2g orbitals.
Octahedral Complexes
The s-orbital of the metal is spherically symmetric.
The three p-orbitals lie along the xyz axes, Î point directly towards the
ligands Î Therefore they all remain degenerate.
eg subset x x
dx2-y2
y dz2 z z
t2g subset x x y
X = I-, Br-, Cl-, H2O and NH3 the colours o cta h ed ral
field
free io n tetra h ed ra l
fie ld
I- < Br- < SCN- ~ Cl- < F- < OH- ~ ONO- < C2O42- < H2O <
NCS- < EDTA4- < NH3 ~ pyr ~ en < bipy < phen < CN- ~ CO
weak-field ligand. E.g. Cl- Î Low energy transition Î Δ = small
Pt Ir Rh Co Cr Fe Fe Co Ni Mn
4+ > 3+ > 3+ > 3+ > 3+ > 3+ > 2+ > 2+ > 2+ > 2+
• Electrons are added to a subshell with the same value of the spin
quantum number until each orbital in the subshell has at least one
electron Î least electrostatic repulsion.
• If Δ < P Î Δ is small, weak field ligand Îe-s spread out among all
d-orbitals before any pairing, e.g. t2g and eg for octahedral CF Î
High-spin complex Î weak field Î outer sphere.
Octahedral electron configuration of octahedral TM complexes
•Îfor d1, d2, d3 and d8, d9, d10 Î the ligand type has same effect on
the d-orbital electron configuration.
•Î for CFSE calculation, strong or weak field ligand will be same.
d1 t2g1eg0 d8 t2g6eg2
d2 t2g2eg0 t2g6eg3
d9
d4 t2g3eg1 t2g4eg0
d5 t2g3eg2 t2g5eg0
d6 t2g4eg2 t2g6eg0
t2g5eg2 t2g6eg1
d7
Δ < P High spin Δ > P Low spin
Crystal–Field Stabilisation Energy (CFSE)
CFT predicts stabilisation for some electron configurations in the d
orbitals.
For an octahedral complex with d orbital configuration t2gxegy, with
respect to the barycentre:
(1) [Fe(CN)6]3-
(2) [FeF6]3-
(3) [Co(H2O)6]+3
•(4) [Co(CN)6]-3
•(5) [Co(NH3)6]+3
•(6) [Co(en)3]+3
a) d4 high spin.
Q2. Given a Dq value of 1040 and 3140 cm-1 for high spin and low
spin d6 ion respectively, determine the CFSE in the following
configurations if the pairing energy P = 17,600 cm-1:
a ) weak field
b) strong field
Q1. a) d4 high spin.
Configuration = t2g3; eg1. Therefore from CFSE = (-4x +6y)Dq + P
CFSE = -4 x 3 + 6 = -6Dq = -12,600cm-1 ; remember for high spin
up to d5 configuration P = 0
b) d6 in a strong field
Configuration = t2g6. Therefore from CFSE = (-4x)Dq + 3P
CFSE = -4 x 6 = -24Dq + 3P = -22,560cm-1
Tetrahedral complexes
Note: For tetrahedral complexes, those orbitals which point towards the
edges (dxy, dyz and dxz) Î e subset are raised to energy higher than
those which point towards the faces Î t2 subset.
1.0
Octahedral Î d3 ; d8 then
d4 and d9 0.8
)
o
OSPE OSPE
Tetrahedral (?) Î d1; d6 and
CFSE (units of
tetrahedral
d2; d7 0.6
In an octahedral crystal field, the t2g orbitals occur at lower energy than
the eg orbitals.
Only important for odd number occupancy of the eg level Î eg1 or eg3.
• Hence the degeneracy of the eg levels is lifted Î ligands along the axes
experience different shielding effects Î 2 e-s vs. 1 e-.
• Resulting in z -axis contraction (dx2-y2 2 dz2 1) or elongation (dx2-y2 1 dz2 2).
As the z axis elongation increases Î the energy of the dz2 orbital drops
lower than the dxy orbital which along with dx2-y2 orbital rises in energy.
X'
X X Cu---X Cu---X΄
2+
X = Cl 2.30 2.95
Cu
X = Br 2.40 3.18
X X
X=F 1.93 2.27
X'
Tetragonally distorted complexes: the Jahn-Teller Effect
• Therefore many Cu2+ complexes are tetragonal even with six identical
ligands, e.g. [Cu(H2O)6]2+.
• No distortion for t2g3, t2g3 eg2 , t2g6, t2g6 eg2 , t2g6 eg4 .
•Important cases of distortion are: t2g3 eg1 (high spin Cr2+ and Mn3+) and
t2g6 eg1 (low spin Co2+ and Mn3+)
Tetragonally distorted complexes: the Jahn-Teller Effect
dx2-y2
dx2-y 2
dx2-y 2
eg
dz 2 dxy
dz 2
dz 2
dxy dxy
t2g
dxz
dxz dyz
dyz dxz
dyz
Mostly formed by metals with d8 ions with strong field ligands, e.g.
[NiII(CN)4]2-. Note that [NiIIX4]2- forms tetrahedral complexes, why?
• We have already seen that on purely e-static grounds, the order of the
spectrochemical series is unviable, e.g. we expect CO < H2O < C2O42- <
EDTA4- Î this is however not the case.
• Evidence from NMR & ESR Î unpaired e-n density on the ligands Î
sharing of e-ns Î strong evidence for M-L covalency.
s
z
z
+ y
y
+
x x
-
-
Pz
z
z
y
y
- + x - + x t2g:
Px
Non
z
z bonding
+
y
x
+
y
x
Orbitals
Remain
-
-
Py
localised
z z z
z on metal
atom
+ y + y y y
- - -
- - x - x
+ +
x + + x
- -
-
-
+
+
dz2 dx2-y2
Oh σ bonding
In LFT the building up principle is
used in conjunction with a molecular
energy level diagram constructed from
metal orbitals and symmetry adapted
linear combination of atomic orbitals
(SALC).
For an octahedral geometry:
Six SALC with σ symmetry interact
with the metal orbitals
The orbitals of the central metal atom
divide by symmetry into 4 sets, viz:
Singly degenerate s a1g
Triply degenerate p t1u
Doubly degenerate d eg Typical molecular energy levels diagram
Triply degenerate d t2g of an octahedral complex showing the
frontier orbitals in the tinted box
Oh σ bonding
• Six of these orbitals are bonding molecular orbitals, whose energies are
much lower than those of the original atomic orbitals.
• Another six are antibonding molecular orbitals, whose energies are higher
than those of the original atomic orbitals.
• Note: The d-orbitals of LFT are the molecular orbitals and not the
atomic orbitals of the CFT
• Summary: Oh σ bonding
2. High spin
Clearly show:
• the relative positions of the metal, ligand and complex orbitals
• 10Dq
• placement of electrons in each case
Oh σ bonding
Answer:
Steps for determining d-orbital energy level diagrams for TM complexes:
Antibonding
MOs
4p
4s Δο
Six donor orbitals
6NH3 each donating
3d 2 e-s
2 xy xz yz
x2-y2 z NB MOs
Bonding MOs
Atomic orbitals in metal ion Molecular orbitals Atomic orbitals in ligand ion
Antibonding
MOs
4p
4s Δο
Six donor orbitals
6 F- each donating
3d 2 e-s
2 xy xz yz NB MOs
x2 -y2 z
Atomic orbitals in metal ion Molecular orbitals Atomic orbitals in ligand ion
Summary:
strong σ- or π-donor
Î weak field ligands.
π-acceptors Î strong
π acceptor ligands field ligands.
π donor ligands
higher in E than t2g. lower in E than t2g.
Increasing Δo →
π donor < weak π donor < no π effects < π acceptor
e.g. I-, Br- Cl- F- H2O NH3 PR3, CO