Descriptive Ligand Field Theory

CHEMICAL BONDS
recall that (1) the "chemical glue" that "binds" two atoms has its
origin in the electrons shared by and located between those two atoms, and (2) electrons
reside in orbitals. Accordingly, knowledge of orbital locations informs where electrons
reside, and that's where bonds will be found. Consequently, knowledge of TM vs orbital
shapes, locations and names are very important to arguments that follow:
Six-coordinate Complexes in an Oh Field

C.N. = 6 and pt. gp. symmetry = Oh

d orbitals in Oh pt. gp. symmetry (a char.table look-up)

d z and d x y transform as the eg two-dimensional irreducible representation.
d xy , d xz , d yz transform as the t2 g three-dimensional irreducible representation

transformation properties of
2

L1

Consider six ligands positioned at Oh sites as

they approach a TM atom/ion to form an
Oh coordination complex, as shown to the right:
Now superimpose on this diagram the five
d orbitals. Note that orientation of the

dz

and

dx y
2

pair allows for greater

+z
TM

L6
L5

+x

L2
L3
+y

L4

interaction with ligand orbitals , then does

the d xy , d xz , d yz set, which has lobes oriented between incoming ligands. Based on
TM to ligand e-e repulsions, TM vs electrons in the former set will be perturbed more by ligand
electrons and this leads to a differentiation (splitting) of energies for d orbitals in the complex.
(1)

Sigma-bonded Oh TM Complexes
Transformation properties of sigma-bonding p-type atomic orbitals for six ligands
Using methods met and used in Chapter 5, ligand -bonding orbitals transform as

( bonds ) = a1 g eg t1u
the eg symmetry orbitals, i.e.,
d z and d x y of the TM.
The TM d xy , d xz , d yz are
2

The only TM - ligand bonding interaction involves

eg

non-bonding in this case. The MO

t2g
diagram for a sigma bonded Oh TM
complex is shown as Figure 10-5 on
page 321. Isolation of TM d orbitals from this diagram shows the above pattern. The
energy difference between eg and t2 g TM orbitals in Oh complexes is labeled

and is represented by the arrow in the above diagram. The MAGNITUDE of the
energy difference
can vary and depends on (a) inherent bonding strength of the
ligand, and (b) charge of the TM ion.

Energy is conserved in the splitting, so the net destabilization of the

eg

set (two

t2 g set (three orbitals). Or,

3

2 x (destabiliz ) 3 x
( stabiliz) 0
5

Applying factors of (3 / 5) and ( -2 / 5) to electrons in eg and t2 g sets respectively,

orbitals) is offset by the stabilization of the

gives the Ligand Field Stabilization Energy.

LFSE can be used to show which

particular d configurations will be more (or less) favored for Oh complex formation.
Refer to text Table 10-5 on page 325, and the following development
n

d 1 [as in Ti(III)]

LFSE = (3/5)[ 0 ] + (-2/5)[ 1 ] = -2/5

d 2 [as in Ti(II),

LFSE = (3/5)[ 0 ] + (-2/5)[ 2 ] = -4/5

V(III) ]

d 3 [as in V(II),

LFSE = (3/5)[ 0 ] + (-2/5)[ 3 ] = -6/5

Cr(III) ]

Two situations arise for d through d depending on the MAGNITUDE of

.
When energy of
is small, relative to energy required for electron pairing, then a
WEAK FIELD (with respect to ligand bonding strength) or HIGH SPIN (with respect to
number of unpaired electrons) condition prevails and so the maximum number of
unpaired electrons will be present.
When energy of
is large, relative to energy required for electron pairing, then a
3

o
o

STRONG FIELD or LOW SPIN condition prevails and the

t2 g set is filled before the eg .

Consider the following diagrams and LFSE's

WEAK FIELD

STRONG FIELD

[as in Cr(II),
Mn(III) ]

LFSE = (3/5)[ 1 ] + (-2/5)[ 4 ] = -3/5

LFSE = (3/5)[ 0 ] + (-2/5)[ 4 ] = -8/5

o (weak field) o (strong field)

Notice that the d weak field case results in FOUR unpaired electrons, but the strong field
case has only TWO unpaired electrons. So measurements of magnetic moments are used to
identify and distinguish between strong field and weak field ligands.
4

Convince yourself that the following results would be obtained for d d,

, d cases
[ WEAK FIELD ] LFSE
[ STRONG FIELD ]LFSE
n
5

d
d6
d7
5

-10/5

-2/5

-12/5

-4/5

-9/5

d vse, only weak field cases are possible so they would be as indicated below.
-6/5 2
and
-3/5
1
d
d9
6
5
LFSE are largest for d in a strong field, and zero for d in a weak field. This information can
For 8 and 9
8

be used to account for some observations in the accumulated data presented at the beginning
of the hour: Co(III) has the largest hydration energy , and its aqua complex is a
field case. Mn(II) and Fe(III) have lowest hydration energies, and they both are
cases having LFSE = 0.

d 6 strong
d 5 weak field

Magnetic moments are very informative in identifying ox.sts. and field strengths of complexes.
Consider some information about iron complexes. Octahedral complexes of Fe(II), a
can be strong field/low spin with n =0, or weak field/high spin with n =4. Octahedral

d 6 case,

complexes of Fe(III), a d case, can be strong field/low spin with n =1, or weak field/high spin
with n =5. Magnetic moments for the four situations would be
5

diamagnetic,
(2)

( so ) = 4.9,

( so ) = 1.8,

and

( so ) = 5.9 B.M. respectively.

Pi-bonded Oh TM Complexes
Carbon Monoxide, a pi-acceptor ligand.
Consider the mo diagram for CO, a ten
electron system.

2p
2p

The HOMO is associated more with

carbon, as is the empty pi* LUMO .
The sigma bond from CO to the TM
involves the HOMO, and is why the
bond is TM - C instead of TM - O.

2s

2s

O
Energy of the empty pi* LUMO is
similar to that of the TM d vse, and more
importantly, they are symmetry matched, so
bonding between them is possible. In this instance however, the TM furnishes
electrons to the empty pi* LUMO, in a manner known as "back-bonding".

The combination of a sigma bond (donation from C in CO to the TM) and pi-bond (backbonding from TM to empty pi* LUMO in CO) makes for exceptionally strong net
bonding. It is the reason for the toxicity of CO which binds so strongly to heme iron in
blood that it can no longer process oxygen. Cyanide anion is isoelectronic with CO and
is also an excellent pi-acceptor ligand. Pi-acceptor ligands are strong field ligands.
Compare CO and CN 1 - to chloride anion, Cl 1 - . Chloride anion has a complete octet
of vse; all of its vs are filled so it cannot accept (pi) electrons from TM. However, it can
donate pi electrons to the TM. But the TM in a complex is already in enough trouble
w/r to electrons and doesn't need any more. Consequently, pi-donor ligands like
chloride anion are weak field ligands; they present too much electron density to the TM.
(3)

Relative Bonding Strengths of Ligands - The Spectrochemical Series

When the bonding effects ( i.e.,

values) of series of ligands are compared for
similar TM's, and then arranged in order of magnitudes of
, a qualitative sequence
of ligands results that is called the Spectrochemical Series. A simple example follows:
STRONG FIELD
CO CN1 - o-phen
pi-acceptor ligands

NO 2

1-

MODERATE FIELD
en NH 3

H2 O

1-

RCO 2

sigma donor ligands

1-

OH

1-

WEAK FIELD
Cl

1-

Br

1-

1-

pi-donor ligands

The effect of larger

values can be demonstrated by the color of coordination
complexes. Consider two complexes of Ni(II), the hexaaqua and hexaammine
complexes. As will become apparent soon, Ni(II), a d system, displays a three-band
absorption spectrum. The hexaaqua complex is green and the hexaammine blue.
These colors are observed b/c the energies they represent are not absorbed, as
shown in the following diagram of the visible range of energies
8

Visible region of the

electromagnetic
spectrum
[ Ni ( H 2O ) 6 ] 2 +
complex, absorbs
energies (in black)
and appears green
in color.
[ Ni ( NH 3 ) 6 ] 2 +
complex, absorbs
energies (in black)
and appears blue
in color.
In both spectra the color is due to the three-band absorption system of the nickel(II) ion
However, ammonia is a stronger field ligand than water so the 3 bands absorb at higher
energies. This shifts the transparent "window" between the center and right absorption
bands to higher energies and imparts a blue color to the ammine complex.

Water is classified as a ligand of moderate/weak donating ability, so it would be

anticipated that aqua complexes are WEAK FIELD / HIGH SPIN cases. Indeed that is
found to be the case , except for one FROTM ion. Only one TM cation forms a strong
field complex with water as ligand, and that is Co(III), a d system.
6

strong field has the highest LFSE . Complexes of

Four-coordinate Complexes in a Square-Planar Field

Recall that

d6

d 6 strong field are diamagnetic.

C.N. = 4 and pt. gp. symmetry =

D4 h

d orbitals in D4 h pt. gp. symmetry (a char.table look-up)

d z transforms as the a1 g irreducible representation
d x y transforms as the b1 g irreducible representation.
d xy transforms as the b2 g irreducible representation, and
d xz , d yz transform as the eg two-dimensional irreducible representation

transformation properties of
2

+z

Consider four ligands in a square-planar

arrangement approaching on the x and

y axes.

Clearly the

dx y
2

most directly in-line with the ligands and

has the highest energy. Remaining d
orbitals would be affected in the following
order d xy then d 2 and lastly the d xz ,
z

L4

would be

+x

d yz

L3

TM

+y

L1

pair. This leads to the splitting pattern

as shown to the right. The numbers indicate the

ordering of entering electrons into this pattern.
Ni(II), a

L2

b1g

d 8 system, forms square-planar complexes.

Introducing 8 electrons into the sq-planar pattern

results in a diamagnetic condition. This feature
allows identification and differentiation of sq-planar
Ni(II) complexes from Oh Ni(II) complexes because
the Oh compounds will be paramagnetic with
( so ) =2.83 B.M.

1,3

7,8

b2g

5,6

a1g
2,4

eg

All available information is used when characterizing coordination compounds, including

chemical analysis, magnetic moments, conductances, and (from the next chapter)
absorption spectra. So while it may be possible to differentiate sq-planar Ni(II) with four
donor atoms, from Oh Ni(II) with six donor atoms by chemical analysis alone, all
information available is collected and applied to the problem. Differences in magnetic
moments for sq-planar and Oh Ni(II) offers additional reliable information for making
the determination.

Four-coordinate Complexes in a Tetrahedral Field

C.N. = 4 and pt. gp. symmetry =

Td

transformation properties of d orbitals in Td pt. gp. symmetry (a char.table look-up)

d 2 and d x 2 y2 transform as the e two-dimensional irreducible representation.
z

d xy , d xz , d yz

transform as the

Note in Td symmetry there are no

inversion center.

or

t2

three-dimensional irreducible representation

u subscripts.

In a Td symmetry field, the splitting pattern

for the five d orbitals is as shown to the right.
Note that it is the inverse of the Oh splitting
pattern.

This is b/c in Td symmetry there is no

t2
e

The energy difference between the two levels is labeled t and is represented by the arrow
in the diagram. Because there are only four donor atoms the Td field is less than an Oh field.
In fact it can be shown that

4
t o .
9

Consequently, Td complexes are always

WEAK FIELD / HIGH SPIN cases.

Ni(II) also forms Td complexes as well as Oh and sq-planar complexes, and even fivecoordinate complexes. Its coordination depends very much on the ligand itself. One of the fun
parts of coordination chemistry is in the designing and subsequent preparation of specific
ligand types to cause formation of a complex having a particular geometrical arrangement.
Chemical analysis and magnetic moment determinations often allows differentiation between
six-coordinate and four-coordinate complexes, and in the latter case, between tetrahedral and
square-planar geometries.