5.

04, Principles of Inorganic Chemistry II

Lecture 17: AOM for ML
n
Ligand Fields
Consider a ligand positioned arbritrarily about the metal
z
M


We can imagine placing the ligand on the metal z axis
(with x and y axes of M and L also aligned) and then
L
rotate it on the surface of a sphere (thus maintaining
(x
L
, y
L
, z
L
)
M-L distance) to its final coordinate position.
y
x
Within the reference frame of the ligand:
z
1
z
L
x
L
z
L
y
L y
L y
L
z
2
x
L
R() R()
rock rotate
y
2 about Z about Z
x y
1
x
1
x
2
related by a coordinate
transformation
S
ML
in complex S
ML
( and ) = 1
z
y


z
L
x
L
2
z
yz
xz
xy
2 2
x -y
F (, )
2 2 2
z
2
y
2
z
2
x
2
z
2
x
2
y
2
x
2
-y
2
1
4
1 +3cos2
( )
0

3
2
sin2
0
3
4
1 cos2
( )
3
sin sin2
coscos sincos2 -cossin
1
sin sin2
2
2
3
cos sin2
-sincos coscos2 sinsin
1
cos sin2
2
2
3
4
sin2 1 cos2
( )
cos2sin
1
2
sin2 sin2 cos2cos
1
4
sin2 3 +cos2
( )
3
4
cos2 1 cos2
( )
-sin2sin
1
2
cos2 sin2 -sin2cos
1
4
cos2 3 +cos2
( )
5.04, Principles of Inorganic Chemistry II Lecture 17
Page 1 of 5
MIT Department of Chemistry
For ligands in an octahedral complex
Ligand 1 2 3 4 5 6
y


0
0
90
0
90
90
90
180
90
270
180
0
1
4
3
6
2
5
z
x
For d
z
2
for L
y
2
z
2

2
d
z
2
=
1
(
1+ 3cos2
)
d
z
2
2
+ 0d
3
sin2d
x
2
z
2

d
2


1
0 0 0
3

d
z
2

4 2

z

2 2

2

d
yz
0 0 0 1 0

d
y
2
z
2

+ 0d
x
2
y
2
+
4
3
(
1 cos2
)
+
2
3
d
x
2
2
y
2
2

d
xz

0 0 1 0 0

d
x
2
z
2

d
xy
0 1 0 0 0

d
x y

2 2
2 2
2
=
1
d
2
+ 0d
y
2
z
2
+ 0d
x
2
z
2
+ 0d
x
2
y
2
+
3
d
2 2

d
x y

2
3
0 0 0
2
1

d
x
2
y
2

2
z
2
2
x
2
y
2
2
continuing other elements of the transformation
matrix may be obtained
2
1 3 1 3
Ed
2
=S
ML
= d
2
+ d
2 2
=

+

z
4
z
2
4
x
2
y
2
4 4
Following the same procedure. Other transformation matrices of L
i
:
for other d-orbitals, E(di) is
E d
yz

-
1 3
( )
= e


0 0 0
1 0 0 0 0

2 2


E d
xz )
= e

0 1 0 0 0

0 0 -1 0 0
(

E d
xy)
= e

L
1
:


0 0 1 0 0

L
3
:

0 0 0 1 0

0 0 0 1 0

0 -1 0 0 0
(
2 2
)
=
3

1




2
3 1
2

E d e + e
0 0 0 0 1

0 0 0 -
x y
4 4

-
1
0 0 0
3
-
1
0 0 0
3

1 0 0 0 0


2 2

2 2


0 0 0 1 0 0 0 1 0 0

0 -1 0 0 0

L
4
:

0 0 1 0 0

L
5
:

0 0 0 -1 0

L
6
:

0 0 1 0 0



0 1 0 0 0 0 -1 0 0 0

0 0 0 -1 0

3 3 1


2
0 0 0
1
2


2
0 0 0 -
2

0 0 0 0 1

5.04, Principles of Inorganic Chemistry II Lecture 17
Page 2 of 5
Squaring the coefficients for each of the ligands:
L1 L2 L3 L4 L5 L6 E
TOTAL
1 3 1 3 1 3 1 3
E(d
2
) e

e

+ e

e

+ e

e

+ e

e

+ e

e

= 3e

+ 3e

z
4 4 4 4 4 4 4 4
E(d
yz
) e

e

e

e

e

e

= 4e

+ 2e

E(d
xz
) e

e

= 4e

+ 2e

E(d
xy
) e

e

= 4e

+ 2e

3 1 3 1 3 1 3 1
E(d
x
2
y
2
)
e

e

+ e

e

+ e

e

+ e

e

+ e

e

= 3e

+ 3e

4 4 4 4 4 4 4 4
As mentioned above e

<<e

or e

thus e

may be ignored. The O
h
energy level
diagram is:
-donor -donor -acceptor
M-L*
4e '

9
9 other L
M-L*
M-L*
M-L*
2 2 2
2 2 2
2 2 2
e
g
(d
x -y
, d
z
) e
g
(d
x -y
, d
z
)
e
g (d
x -y
, d
z
)
3e
3e

M-L*
3e

t
2g
(d
xy
, d
xz
, d
yz
)
n.b.
4e

nd nd
t
2g
(d
xy
, d
xz
, d
yz
)
nd
4e

t
2g (d
xy
, d
xz
, d
yz
)
M-L
6L 6L 6L
3e

' 3e ' 3e '

M-L e
g
M-L e
g
M-L e
g
Note the d-orbital splitting is the same result obtained from the CFT model taught
in Freshman chemistry. In fact the energy parameterization scales directly between
CFT and AOM
10 Dq =
0
= 3e

- 4e

5.04, Principles of Inorganic Chemistry II Lecture 17
Page 3 of 5
A table of angular scaling factors for e and e has been removed due to

copyright considerations.
A list of common structures for two through six
ligands has been removed due to copyright
considerations.
5.04, Principles of Inorganic Chemistry II Lecture 17
Page 4 of 5
Lets use e

and e

parameters to determine the d-energy level splitting diagram for

T
d
complexes
M-L*
M-L*
M-L*
M-L
t
2
(d
xy
, d
xz
, d
yz
)
t
2
(d
xy
, d
xz
, d
yz
)
M-L*
4 8
4 8
t
2
(d
xy
, d
xz
, d
yz
) e + e
e + e
3 9
3

9

M-L* M-L*
4
2 2 2 2 2 2
e (d
x -y
, d
z
)
e
(d
x -y
, d
z
)
3
e
8
8
e n.b.
e

3
3
nd
nd
e (d
x
2
-y
2
, d
z
2
)
nd
8L
M-L
t
2
t
1
8
9
e

8
3
e

e
8L
8
e

9
8
e
t
2
3
M-L
e
nb nb
nb
4L
4L
4L
4 4
e ' e

'
3

3
M-L
t
2 M-L
t
2 M-L t
2
Note that
( \
AT
d
= |
4
e
o
+
8
e

| ~
8
e

=
4
e
o
~
16
e

=
4
(
3e
o
~ 4
)
=
4
A
0
\
3 9
!
3 3 9 9 9

This is the result from CFT
(inversion of e/t
2
leads to
the (-) sign)

4
T
d
=
0
9
5.04, Principles of Inorganic Chemistry II Lecture 17
Page 5 of 5