Black plate (556,1)

orbital on the metal centre can accept a pair of electrons

from a ligand to form a -bond. The choice of particular p
or d atomic orbitals may depend on the denition of the
axes with respect to the molecular framework, e.g. in linear
ML
2
, the ML vectors are dened to lie along the z axis.
We have included the cube in Table 20.1 only to point out
the required use of an f orbital.
Applying VB theory
We illustrate the applications and limitations of VB theory
by considering octahedral complexes of Cr(III) (d
3
) and
Fe(III) (d
5
) and octahedral, tetrahedral and square planar
complexes of Ni(II) (d
8
). The atomic orbitals required for
hybridization in an octahedral complex are the 3d
z
2 ,
3d
x
2
y
2 , 4s, 4p
x
, 4p
y
and 4p
z
(Table 20.1); these orbitals
must be unoccupied so as to be available to accept six pairs
of electrons from the ligands. The Cr
3
ion has three
unpaired electrons and these are accommodated in the
3d
xy
, 3d
xz
and 3d
yz
orbitals:
Fig. 20.1 (a) The six ML vectors of an octahedral complex ML
6

n
can be dened to lie along the x, y and z axes. (b) The ve
d orbitals; the d
z
2 and d
x
2
y
2 atomic orbitals point directly along the axes, but the d
xy
, d
yz
and d
xz
atomic orbitals point between them.
Table 20.1 Hybridization schemes for the -bonding frameworks of dierent geometrical congurations of ligand donor atoms.
Coordination
number
Arrangement of donor
atoms
Orbitals hybridized Hybrid orbital
description
Example
2 Linear s, p
z
sp AgNH
3

3 Trigonal planar s, p
x
, p
y
sp
2
HgI
3

4 Tetrahedral s, p
x
, p
y
, p
z
sp
3
FeBr
4

2
4 Square planar s, p
x
, p
y
, d
x
2
y
2 sp
2
d NiCN
4

2
5 Trigonal bipyramidal s, p
x
, p
y
, p
z
, d
z
2 sp
3
d CuCl
5

3
5 Square-based pyramidal s, p
x
, p
y
, p
z
, d
x
2
y
2 sp
3
d NiCN
5

3
6 Octahedral s, p
x
, p
y
, p
z
, d
z
2 ; d
x
2
y
2 sp
3
d
2
CoNH
3

3
6 Trigonal prismatic s, d
xy
, d
yz
, d
xz
, d
z
2 , d
x
2
y
2
or
s, p
x
, p
y
, p
z
, d
xz
, d
yz
sd
5
or
sp
3
d
2
ZrMe
6

2
7 Pentagonal bipyramidal s, p
x
, p
y
, p
z
, d
xy
, d
x
2
y
2 , d
z
2 sp
3
d
3
VCN
7

4
7 Monocapped trigonal
prismatic
s, p
x
, p
y
, p
z
, d
xy
, d
xz
, d
z
2 sp
3
d
3
NbF
7

2
8 Cubic s, p
x
, p
y
, p
z
, d
xy
, d
xz
, d
yz
, f
xyz
sp
3
d
3
f PaF
8

3
8 Dodecahedral s, p
x
, p
y
, p
z
, d
z
2 , d
xy
, d
xz
, d
yz
sp
3
d
4
MoCN
8

4
8 Square antiprismatic s, p
x
, p
y
, p
z
, d
xy
, d
xz
, d
yz
, d
x
2
y
2 sp
3
d
4
TaF
8

3
9 Tricapped trigonal
prismatic
s, p
x
, p
y
, p
z
, d
xy
, d
xz
, d
yz
, d
z
2 , d
x
2
y
2 sp
3
d
5
ReH
9

2
556 Chapter 20 . d-Block chemistry: coordination complexes
Black plate (557,1)
With the electrons from the ligands included and a hybridi-
zation scheme applied for an octahedral complex, the
diagram becomes:
This diagram is appropriate for all octahedral Cr(III)
complexes because the three 3d electrons always singly
occupy dierent orbitals.
For octahedral Fe(III) complexes, we must account for
the existence of both high- and low-spin complexes. The
electronic conguration of the free Fe
3
ion is:
For a low-spin octahedral complex such as FeCN
6

3
, we
can represent the electronic conguration by means of the
following diagram where the electrons shown in red are
donated by the ligands:
For a high-spin octahedral complex such as FeF
6

3
, the
ve 3d electrons occupy the ve 3d atomic orbitals (as in the
free ion shown above) and the two d orbitals required for
the sp
3
d
2
hybridization scheme must come from the 4d set.
With the ligand electrons included, valence bond theory
describes the bonding as follows leaving three empty 4d
atomic orbitals (not shown):
This scheme, however, is unrealistic because the 4d orbitals
are at a signicantly higher energy than the 3d atomic
orbitals.
Nickel(II) (d
8
) forms paramagnetic tetrahedral and octa-
hedral complexes, and diamagnetic square planar complexes.
Bonding in a tetrahedral complex can be represented as
follows (ligand electrons are shown in red):
and an octahedral complex can be described by the diagram:
in which the three empty 4d atomic orbitals are not shown.
For diamagnetic square planar complexes, valence bond
theory gives the following picture:
Valence bond theory may rationalize stereochemical and
magnetic properties, but only at a simplistic level. It can
say nothing about electronic spectroscopic properties or
about the kinetic inertness (see Section 25.2) that is a char-
acteristic of the low-spin d
6
conguration. Furthermore, the
model implies a distinction between high- and low-spin
complexes that is actually misleading. Finally, it cannot tell
us why certain ligands are associated with the formation of
high- (or low-)spin complexes. We therefore move on to
alternative approaches to the bonding.
20.3 Crystal eld theory
A second approach to the bonding in complexes of the d-
block metals is crystal eld theory. This is an electrostatic
model and simply uses the ligand electrons to create an
electric eld around the metal centre. Ligands are considered
as point charges and there are no metalligand covalent
interactions.
CHEMICAL AND THEORETICAL BACKGROUND
Box 20.1 Valence bond theory: a historical note
In the early use of VB theory, complexes in which the
electronic conguration of the metal ion was the same as
that of the free gaseous atom were called ionic complexes,
while those in which the electrons had been paired up as
far as possible were called covalent complexes. Later, rst
row metal complexes in which ligand electrons entered 3d
orbitals (as in FeCN
6

3
) were termed inner orbital
complexes, and those in which 4d orbitals were occupied
(as in FeF
6

3
) were outer orbital complexes. The various
terms, all of which may be encountered, relate to one
another as follows:
. high-spin complex ionic complex outer orbital
complex;
. low-spin complex covalent complex inner orbital
complex.
Chapter 20 . Crystal eld theory 557
Black plate (563,1)
Fig. 20.8 Crystal eld splitting diagrams for octahedral (left-hand side) and tetrahedral (right-hand side) elds. The splittings are
referred to a common barycentre. See also Figure 20.2.
M
L
L L
L
L
L
M
L
L L
L
M
L
L L
L
L
L
Octahedral complex Removal of axial
ligands
Square
planar
complex
z
y
x
n+
n+
n+
Fig. 20.9 A square planar complex can be derived from an octahedral complex by the removal of two ligands, e.g. those on the z
axis; the intermediate stage is a JahnTeller distorted (elongated) octahedral complex.
Fig. 20.10 Crystal eld splitting diagrams for some common elds referred to a common barycentre; splittings are given with
respect to
oct
. For tetrahedral splitting, see Figure 20.8.
Chapter 20 . Crystal eld theory 563
Black plate (88,1)
Is there a
h
plane
(perpendicular to the
principal axis)?
Yes; it contains the P and
three F
eq
atoms.
STOP
The point group is D
3h
.
Self-study exercises
1. Show that BF
3
belongs to the D
3h
point group.
2. Show that OF
2
belongs to the C
2v
point group.
Worked example 3.6 Point group assignments: 3
To what point group does POCl
3
belong ?
The structure of POCl
3
is:
O
P
Cl
Cl
Cl
Apply the strategy shown in Figure 3.10:
START
Is the molecule linear? No
Does POCl
3
have T
d
, O
h
or
I
h
symmetry?
No (remember that
although this molecule is
loosely considered as
being tetrahedral in
shape, it does not
possess tetrahedral
symmetry)
Is there a C
n
axis? Yes; a C
3
axis
running along the OP
bond
Are there 3 C
2
axes
perpendicular to the
principal axis? No
Is there a
h
plane
(perpendicular to the
principal axis)? No
Are there n
v
planes
(containing the principal
axis)?
Yes; each contains the
one Cl and the O and P
atoms
STOP
The point group is C
3v
.
Fig. 3.10 Scheme for assigning point groups of molecules and molecular ions. Apart from the cases of n 1 or 1, n most
commonly has values of 2, 3, 4, 5 or 6.
88 Chapter 3 . An introduction to molecular symmetry
Resource section 4
Character tables
The character tables that follow are for the most common point groups encountered in
inorganic chemistry. Each one is labelled with the symbol adopted in the Schoenfies
system of nomenclature (such as C
3v
). Point groups that qualify as crystallographic point
groups (because they are also applicable to unit cells) are also labelled with the symbol
adopted in the International System (or the HermannMauguin system, such as 2/m). In
the latter system, a number n represents an n-fold axis and a letter m represents a mirror
plane. A diagonal line indicates that a mirror plane lies perpendicular to the symmetry axis
and a bar over the number indicates that the rotation is combined with an inversion.
The symmetry species of the p and d orbitals are shown on the right of the tables. Thus,
in C
2v
, a p
x
orbital (which is proportional to x) has B
1
symmetry. The functions x, y, and z
also show the transformation properties of translations and of the electric dipole moment.
The set of functions that span a degenerate representation (such as x and y, which jointly
span E in C
3v
) are enclosed in parentheses. The transformation properties of rotation are
shown by the letters R on the right of the tables. The value of h is the order of the group.
The groups C
1,
C
s
, C
i
C
1
(1) E h = 1
A 1
The groups C
n
C
2
(2) E C
2
h = 2
A 1 1 z, R
z
x
2
, y
2
, z
2
, xy
B 1 1 x, y, R
x
, R
y
yz, zx
C
4
(4) E C
4
C
2
C
4
3
h = 4
A 1 1 1 1 z, R
z
x
2
+ y
2
, z
2
B 1 1 1 1 x
2
y
2
, xy
E
1 1
1 1
i i
i i

(x, y)(R
x
, R
y
) (yz, zx)
C
s
= C
h
(m) E o
h
h = 2
A 1 1 x, y, R
z
x
2
, y
2
, z
2
, xy
A 1 1 z, R
x
, R
y
yz, zx
C
i
= S
2
(1) E i h = 2
A
g
1 1 R
x
, R
y
, R
z
x
2
, y
2
, z
2
, xy, zx, yz
A
u
1 1 x, y, z
C
3
(3) E C
3
C
3
2
r = exp(2i/3) h = 3
A 1 1 1 z, R
z
x
2
+ y
2
, z
2
E
1
1
r r
r r
*
*

(x, y)(R
x
, R
y
) (x
2
y
2
, xy) (yz, zx)
Resource section 4
801
The groups C
nv
C
2v
(2mm) E C
2
o
v
(xz) o
v
(yz) h = 4
A
1
1 1 1 1 z x
2
, y
2
, z
2
A
2
1 1 1 1 R
z
xy
B
1
1 1 1 1 x, R
y
zx
B
2
1 1 1 1 y, R
x
yz
C
4v
(4mm) E 2C
4
C
2
2o
v
2o
d
h = 8
A
1
1 1 1 1 1 z x
2
+ y
2
, z
2
A
2
1 1 1 1 1 R
z
B
1
1 1 1 1 1 x
2
y
2
B
2
1 1 1 1 1 xy
E 2 0 2 0 0 (x, y) (R
x
, R
y
) (zx, yz)
C
6v
(6mm) E 2C
6
2C
3
C
2
3o
v
3o
d
h = 12
A
1
1 1 1 1 1 1 z x
2
+ y
2
, z
2
A
2
1 1 1 1 1 1 R
z
B
1
1 1 1 1 1 1
B
2
1 1 1 1 1 1
E
1
2 1 1 2 0 0 (x, y) (R
x
, R
y
) (zx, yz)
E
2
2 1 1 2 0 0 (x
2
y
2
, xy)
The groups D
n
D
2
(222) E C
2
(z) C
2
(y) C
2
(x) h = 4
A 1 1 1 1 x
2
, y
2
, z
2
B
1
1 1 1 1 z, R
z
xy
B
2
1 1 1 1 y, R
y
zx
B
3
1 1 1 1 x, R
x
yz
C
3v
(3m) E 2C
3
3o
v
h = 6
A
1
1 1 1 z x
2
+ y
2
, z
2
A
2
1 1 1 R
z
E 2 1 0 (x, y) (R
x
, R
y
) (x
2
y
2
, xy)(zx, yz)
C
5v
E 2C
5
2C
5
2
5o
v
h = 10, o = 72
A
1
1 1 1 1 z x
2
+ y
2
, z
2
A
2
1 1 1 1 R
z
E
1
2 2cos o 2cos 2o 0 (x, y) (R
x
, R
y
) (zx, yz)
E
2
2 2cos 2o 2cos o 0 (x
2
y
2
, xy)
C
v
E 2C
o
o
v
h =
A
1
(Z
+
) 1 1 1 z x
2
+ y
2
, z
2
A
2
(Z

)
1 1 1 R
z
E
1
() 2 2 cos o 0 (x, y) (R
x
, R
y
) (zx, yz)
E
2
() 2 2 cos 2 o 0 (xy, x
2
y
2
)
D
3
(32) E 2C
3
3C
2
h = 6
A
1
1 1 1 x
2
+ y
2
, z
2
A
2
1 1 1 z, R
z
E 2 1 0 (x, y) (R
x
, R
y
) (x
2
y
2
, xy) (zx, yz)
802
Resource section 4
The groups D
nh
D
2h
(mmm) E C
2
(z) C
2
(y) C
2
(x) i o(xy) o(xz) o(yz) h = 8
A
g
1 1 1 1 1 1 1 1 x
2
, y
2
, z
2
B
1g
1 1 1 1 1 1 1 1 R
z
xy
B
2g
1 1 1 1 1 1 1 1 R
y
zx
B
3g
1 1 1 1 1 1 1 1 R
x
yz
A
u
1 1 1 1 1 1 1 1
B
1u
1 1 1 1 1 1 1 1 z
B
2u
1 1 1 1 1 1 1 1 y
B
3u
1 1 1 1 1 1 1 1 x
D
3h
(6m2) E 2C
3
3C
2
o
h
2S
3
3o
v
h = 12
A
1
1 1 1 1 1 1 x
2
+ y
2
, z
2
A
2
1 1 1 1 1 1 R
z
E 2 1 0 2 1 0 (x, y) (x
2
y
2
, xy)
A
1
1 1 1 1 1 1
A
2
1 1 1 1 1 1 z
E 2 1 0 2 1 0 (R
x
, R
y
) (zx, yz)
D
4h
(4/mmm) E 2C
4
C
2
2C
2
2C
2
i 2S
4
o
h
2o
v
2o
d
h = 16
A
1g
1 1 1 1 1 1 1 1 1 1 x
2
+ y
2
, z
2
A
2g
1 1 1 1 1 1 1 1 1 1 R
z
B
1g
1 1 1 1 1 1 1 1 1 1 x
2
y
2
B
2g
1 1 1 1 1 1 1 1 1 1 xy
E
g
2 0 2 0 0 2 0 2 0 0 (R
x
, R
y
) (zx, yz)
A
1u
1 1 1 1 1 1 1 1 1 1
A
2u
1 1 1 1 1 1 1 1 1 1 z
B
1u
1 1 1 1 1 1 1 1 1 1
B
2u
1 1 1 1 1 1 1 1 1 1
E
u
2 0 2 0 0 2 0 2 0 0 (x, y)
D
5h
E 2C
5
2C
5
2
5C
2
o
h
2S
5
2S
5
2
5o
v
h = 20, o = 72
A
1
1 1 1 1 1 1 1 1 x
2
+ y
2
, z
2
A
2
1 1 1 1 1 1 1 1 R
z
E
1
2 2cos o 2cos 2o 0 2 2cos o 2cos 2o 0 (x, y)
E
2
2 2cos 2o 2cos o 0 2 2cos 2o 2cos o 0 (x y
2
, xy)
A
1
1 1 1 1 1 1 1 1
A
2
1 1 1 1 1 1 1 1 z
E
1
2 2cos o 2cos 2o 0 2 2cos o 2cos 2o 0 (R
x
, R
y
) (zx, yz)
E
2
2 2cos 2o 2cos o 0 2 2cos 2o 2cos o 0
Resource section 4
803
The groups D
nh
(continued)
D
6h
(6/mmm) E 2C
6
2C
3
C
2
3C
2
3C
2
i 2S
3
2S
6
o
h
3o
d
3o
v
h = 24
A
1g
1 1 1 1 1 1 1 1 1 1 1 1 x
2
+ y
2
, z
2
A
2g
1 1 1 1 1 1 1 1 1 1 1 1 R
z
B
1g
1 1 1 1 1 1 1 1 1 1 1 1
B
2g
1 1 1 1 1 1 1 1 1 1 1 1
E
1g
2 1 1 2 0 0 2 1 1 2 0 0 (R
x
, R
y
) (zx, yz)
E
2g
2 1 1 2 0 0 2 1 1 2 0 0 (x
2
y
2
, xy)
A
1u
1 1 1 1 1 1 1 1 1 1 1 1
A
2u
1 1 1 1 1 1 1 1 1 1 1 1 z
B
1u
1 1 1 1 1 1 1 1 1 1 1 1
B
2u
1 1 1 1 1 1 1 1 1 1 1 1
E
1u
2 1 1 2 0 0 2 1 1 2 0 0 (x, y)
E
2u
2 1 1 2 0 0 2 1 1 2 0 0
D
h
E C
2
2C
o
i o
v
2S
o
h =
A
1g
(Z
g
+
) 1 1 1 1 1 1 z
2
, x
2
+ y
2
A
1u
(Z
u
+
) 1 1 1 1 1 1 z
A
2g
(Z
g

) 1 1 1 1 1 1 R
z
A
2u
(Z
u

) 1 1 1 1 1 1
E
1g
(
g
) 2 0 2cos o 2 0 2cos o (R
x
, R
y
) (zx, yz)
E
1u
(
u
) 2 0 2cos o 2 0 2cos o (x, y)
E
2g
(
g
) 2 0 2cos 2o 2 0 2cos 2o (xy, x
2
y
2
)
E
2u
(
u
) 2 0 2cos 2o 2 0 2cos 2o

The groups D
nd
D
2d
= V
d
(42m) E 2S
4
C
2
2C
2
2o
d
h = 8
A
1
1 1 1 1 1 x
2
+ y
2
, z
2
A
2
1 1 1 1 1 R
z
B
1
1 1 1 1 1 x
2
y
2
B
2
1 1 1 1 1 z xy
E 2 0 2 0 0 (x, y) (R
x
, R
y
) (zx, yz)
D
3d
(3m) E 2C
3
3C
2
i 2S
6
3o
d
h = 12
A
1g
1 1 1 1 1 1 x
2
+ y
2
, z
2
A
2g
1 1 1 1 1 1 R
z
E
g
2 1 0 2 1 0 (R
x
, R
y
) (x
2
y
2
, xy) (zx, yz)
A
1u
1 1 1 1 1 1
A
2u
1 1 1 1 1 1 z
E
u
2 1 0 2 1 0 (x, y)
804
Resource section 4
The groups D
nd
(continued)
D
4d
E 2S
8
2C
4
2S
8
3
C
2
4C
2
4o
d
h = 16
A
1
1 1 1 1 1 1 1 x
2
+ y
2
, z
2
A
2
1 1 1 1 1 1 1 R
z
B
1
1 1 1 1 1 1 1
B
2
1 1 1 1 1 1 1 z
E
1
2 2 0 2 2 0 0 (x, y)
E
2
2 0 2 0 2 0 0 (x
2
y
2
, xy)
E
3
2 2 0 2 2 0 0 (R
x
, R
y
) (zx, yz)
The cubic groups
T
d
(43m) E 8C
3
3C
2
6S
4
6o
d
h = 24
A
1
1 1 1 1 1 x
2
+ y
2
+ z
2
A
2
1 1 1 1 1
E 2 1 2 0 0 (2z
2
x
2
y
2
, x
2
y
2
)
T
1
3 0 1 1 1 (R
x
, R
y
, R
z
)
T
2
3 0 1 1 1 (x, y, z) (xy, yz, zx)
O
h
(m3m) E 8C
3
6C
2
6C
4
3C
2
(=C
4
2
) i 6S
4
8S
6
3o
h
6o
d
h = 48
A
1g
1 1 1 1 1 1 1 1 1 1 x
2
+y
2
+ z
2
A
2g
1 1 1 1 1 1 1 1 1 1
E
g
2 1 0 0 2 2 0 1 2 0 (2z
2
x
2
y
2
, x
2
y
2
)
T
1g
3 0 1 1 1 3 1 0 1 1 (R
x
, R
y
, R
z
)
T
2g
3 0 1 1 1 3 1 0 1 1 (xy, yz, zx)
A
1u
1 1 1 1 1 1 1 1 1 1
A
2u
1 1 1 1 1 1 1 1 1 1
E
u
2 1 0 0 2 2 0 1 2 0
T
1u
3 0 1 1 1 3 1 0 1 1 (x, y, z)
T
2u
3 0 1 1 1 3 1 0 1 1
The icosahedral group
I E 12C
5
12C
5
2
20C
3
15C
2
h = 60
A
1
1 1 1 1 1 x
2
+ y
2
+ z
2
T
1
3
1
2 (1+ 5)
1
2 (1 5) 0 1
(x, y, z)
(R
x
, R
y
, R
z
)
T
2
3
1
2
(1 5)
1
2 (1+ 5) 0 1
G 4 1 1 1 0
H 5 0 0 1 1 (2z
2
x
2
y
2
, x
2
y
2
, xy, yz, zx)
Further information: www.oxfordtextbooks.co.uk/orc/ichem5e
Resource section 5
Symmetry-adapted orbitals
Table RS5.1 gives the symmetry classes of the s, p, and d orbitals of the central atom of an
AB
n
molecule of the specifed point group. In most cases, the z-axis is the principal axis of
the molecule; in C
2v
the x-axis lies perpendicular to the molecular plane.
The orbital diagrams that follow show the linear combinations of atomic orbitals on the
peripheral atoms of AB
n
molecules of the specifed point groups. Where a view from above
is shown, the dot representing the central atom is either in the plane of the paper (for the
D groups) or above the plane (for the corresponding C groups). Different phases of the
atomic orbitals (+1 or 1; amplitudes) are shown by different colours. Where there is a
large difference in the magnitudes of the orbital coeffcients in a particular combination,
the atomic orbitals have been drawn large or small to represent their relative contributions
to the linear combination. In the case of degenerate linear combinations (those labelled
E or T), any linearly independent combination of the degenerate pair is also of suitable
symmetry. In practice, these different linear combinations look like the ones shown here,
but their nodes are rotated by an arbitrary axis around the z-axis.
Molecular orbitals are formed by combining an orbital of the central atom (as in
Table RS5.1) with a linear combination of the same symmetry.
Table RS5.1 Symmetry species of orbitals on the central atom
D
h
C
2v
D
3h
C
3v
D
4h
C
4v
D
5h
C
5v
D
6h
C
6v
T
d
O
h
s A
1
A
1
A
1
A
1g
A
1
A
1
A
1
A
1g
A
1
A
1
A
1g
p
x
B
1
E E E
u
E E
1
E
1
E
1u
E
1
T
2
T
1u
p
y
B
2
E E E
u
E E
1
E
1
E
1u
E
1
T
2
T
1u
p
z
A
1
A
2
A
1
A
2u
A
1
A
2
A
1
A
2u
A
1
T
2
T
1u
d
z
2 A
1
A
1
A
1
A
1g
A
1
A
1
A
1
A
1g
A
1
E E
g
d
x
2
y
2 A
1
E E B
1g
B
1
E
2
E
2
E
2g
E
2
E E
g
d
xy
A
2
E E B
2g
B
2
E
2
E
2
E
2g
E
2
T
2
T
2g
d
yz
B
2
E E E
g
E E
1
E
1
E
1g
E
1
T
2
T
2g
d
zx
B
1
E E E
g
E E
1
E
1
E
1g
E
1
T
2
T
2g
806
Resource section 5
Z
g
H
g
H
u
Z
u
A
1
A
2
B
1
B
2
A
1
B
2
D
h
C
2v
A
1
A
1

A
1
A
2
A
2

D
3h
C
3v
E E
E E
E
A
2

E
A
1
A
1g
A
1
A
2u
A
2
A
2g
D
4h
C
4v
E E
u
E E
g
B
1
B
1g
B
2
B
2g
B
2
B
2u
Resource section 5
807
A
1
A
1

A
1
A
2

A
2
A
2

D
5h
C
5v
E
1
E
1

E
1
E
2
E
2

E
2
E
1

E
2

A
1
A
1g
A
1
A
2u
E
1
E
1u
E
1
E
1g
E
2
E
2u
A
2
A
2g
D
6h
C
6v
B
1
B
1u
E
2
E
2g
B
2
B
2u
B
1
B
2g
808
Resource section 5
O
h
A
1g
E
g
T
1u
T
1u
T
2u
T
2g
T
1g
A
1
T
2
T
d
Resource section 6
TanabeSugano diagrams
This section collects together the TanabeSugano diagrams for octahedral complexes with
electron confgurations d
2
to d
8
. The diagrams, which were introduced in Section 20.4,
show the dependence of the term energies on ligand-feld strength. The term energies E
are expressed as the ratio E/B, where B is a Racah parameter, and the ligand-feld splitting

O
is expressed as
O
/B. Terms of different multiplicity are included in the same diagram
by making specifc, plausible choices about the value of the Racah parameter C, and these
choices are given for each diagram. The term energy is always measured from the lowest
energy term, and so there are discontinuities of slope where a low-spin term displaces a
high-spin term at suffciently high ligand-feld strengths for d
4
to d
8
confgurations. More-
over, the noncrossing rule requires terms of the same symmetry to mix rather than to cross,
and this mixing accounts for the curved rather than the straight lines in a number of cases.
The term labels are those of the point group O
h
.
The diagrams were frst introduced by Y. Tanabe and S. Sugano, J. Phys. Soc. Japan,
1954, 9, 753. They may be used to fnd the parameters
O
and B by ftting the ratios of the
energies of observed transitions to the lines. Alternatively, if the ligand-feld parameters are
known, then the ligand-feld spectra may be predicted.
1. d
2
with C = 4.428B
70
50
40
30
20
10
60
1
G
1
D
1
S
1
1
T
3
2
T
1
1
A
1
E,
1
T
2
3
1
T
0 10 20 30
3
1
T
1
2
T
3
P
3
F
E
/
B
A
O
/B
3
A
2
1
A
1
1
E
2. d
3
with C = 4.502B
70
60
50
40
30
20
10
10 20 30
E
B
/
4
F
2
F
4
P
2
G
2
D
A
O
/B
4
2
A
2
E
2
1
T
2
2
T
4
2
T
4
1
T
2
1
A
4
1
T
2
A
2
810
Resource section 6
3. d
4
with C = 4.611B
10 20 30
E
B
/
3
A
2
3
A
2
3
E
5
E
1
E
3
A
1
1
A
2
1
A
1
1
A
2
1
T
1
3
T
1
3
T
2
1
T
2
5
T
2
70
60
50
40
30
20
10
3
F
3
F
3
G
1
G,
1
I
1
F
3
H
5
D
A
O
/B
t
2g
e
g
t
2g
e
g
t
2g
2 2
3 1
4
4. d
5
with C = 4.477B
70
50
40
30
20
10
60
0 10 20 30
E
/
B
A
O
/B
4
F
2
I
4
G
6
S
4
D
4
A
2
2
A
1
6
A
1
e
g
2
T
2
2
T
2
4
T
2
4
T
1
4
A
1
,
4
E
2
A
2
,
2
T
1
4
E
2
E
3
5
t
2g
t
2g
2
5. d
6
with C = 4.808B
70
50
40
30
20
10
60
0 10 20 30
E
/
B
A
O
/B
1
F
5
D
1
I
3
H
3
F
3
F
3
G
3
A
2
3
T
2
3
T
1
3
A
2
3
A
1
1
A
2
1
A
2
5
E e
g
1
T
2
1
A
1
5
T
2
1
T
1
1
E
3
E
3 3
t
2g
5 1
t
2g
e
g
5 1
t
2g
6
t
2g
e
g
4 2
t
2g
e
g
6. d
7
with C = 4.633B
70
50
40
30
10
60
0 10 20 30
E
/
B
A
O
/B
2
A
2
2
T
2
2
T
1
2
A
1
4
T
1
4
T
1
4
T
1
4
A
2
2
E
4
T
2
2
F
4
P
4
F
2
H
2
G
3 4
t
2g
e
g
4 3
t
2g
e
g
6 1
t
2g
e
g
Resource section 6
811
7. d
8
with C = 4.709B
E
/
B
70
50
20
40
30
10
60
0 10 20 30
A
O
/B
1
S
1
G
1
D
3
P
3
F
1
A
1
1
A
1
1
T
1
1
T
2
1
T
2
3
T
1
3
T
1
3
T
2
3
A
2
1
E
1
E
5 3
t
2g
e
g
6 2
t
2g
e
g