Unit 11 Applications & Limitations of Crystal Field Theory

UNIT 11

APPLICATIONS & LIMITATIONS

OF CRYSTAL FIELD THEORY

Structure
11.1 Introduction 11.3 Limitations of Crystal Field
Theory
Expected Learning Outcomes
11.2 Applications of Crystal Field Molecular Orbital Theory

Theory Nephelauxetic Effect

11.4 Pi-Bonding and Molecular
Lattice Energies Orbital Theory
Ionic Radii 11.5 Summary
Thermodynamic and Related 11.6 Terminal Questions
Aspects of Crystal Fields
11.7 Answers
Heats of Ligation
Site Preference Energies

11.1 INTRODUCTION
In the previous unit you were introduced to crystal field theory. In this unit you
are going to learn about the applications and limitations of the crystal field
theory. The variations in lattice energies, ionic radii, the theromodyamic and
other aspects which cannot be fully explained by crystal field theory will be our
points of discussion. Also, we will study the trends of heats of ligation and site
preference energies and see whether crystal field theory can explain them
totally or not. The molecular orbital theory and the nephelauxetic effect will
also be discussed as they overcome the limitation of the crystal field theory.
We will end our discussion in this unit with pi-bonding and molecular orbital
theory. In this way you will first learn about the applications and then you will
be learning about the limitations of crystal field theory.

Expected Learning Outcomes

After studying this unit you should be able to:
 discuss the applications of crystal field theory, in context with lattice
energies and ionic radii; 31
Block 3 Crystal Field Theory and Its Applications

 understand thermodynamic aspects like heats of ligation and site

preference energies;
 appreciate the limitations of crystal field theory in context with molecular
orbital theory and nephelauxetic effect; and
 discuss pi-bonding and molecular orbital theory.

11.2 APPLICATIONS OF CRYSTAL FIELD

THEORY
In the initial period of the studies on crystal field theory the greatest success
was in explaining magnetic and spectral properties of complexes. Also, a
number of their structural and thermodynamic properties were predicted taking
the crystal field theory as the basis. In this section we will describe some of
these properties from the crystal field point of view. The concepts of crystal
field theory, such as crystal (or ligand) field stabilization energy, are even used
while discussing these properties in the light of molecular orbital theory.

11.2.1 Lattice Energies

Fig. 11.1: Lattice energies of the divalent metal halides of the first series.
Vertical bars indicate e experimental values.
(Source: https://web.iitd.ac.in/~sdeep/Elias_Inorg_lec_2.pdf)

Now you should understand that it was while calculating lattice energies in
transition metal compounds, crystal field stabilization energy was found useful.
Studies showed that lattice energies could be predicted in a better way for ions
such as Na+, K+, Ca2+, Mn2+, and Zn2+ than those for Cr2+, Fe2+, Co2+, Ni2+ and
Cu2+. CFSE is the answer for cases in six-coordinate metal ions where the
calculations do not match. d 0,d 5 (high spin), and d10 configurations who have
CFSE = 0 have no such discrepancies. Now let us study this with the case of
the lattice energies of the halides from CaX2 to ZnX2, where the metal ions
occupy octahedral holes. Look at Fig. 11.2, you see that there is a gradual
decrease in ionic radius from Ca2+ to Zn2+. In similar lines, there should be a
32 gradual and smooth increase in lattice energy based on the Bom-Landé
Unit 11 Applications & Limitations of Crystal Field Theory

equation. If you look at by Fig. 11.2, the curve is not smooth. The ions Ca2+,
Mn2+ and Zn2+ lie on a curve that is nearly a straight one. There are two
minimum points, one in the region of V2+ and the other in the region of Ni2+.
Table 10.3 of previous unit indicates that for a weak octahedral field
(remember that the halide ions are on the weak end of the spectrochemical
series), V 2 (d 3 ) and Ni2 (d 8 ) have the greatest CFSE values (12o). Next
comes the d 2 ,d 4 , d 7 and d 9 ions (having values between 0.6 and 0.8o).
The d 0 , d 5 and d 10 cases have zero CFSE. Even though there are large
experimental errors, the shape of the curve shows this qualitatively.

(a) (b)
2+ 2+
Fig. 11.2: Radii of the a) divalent ions Ca to Zn and (b) the trivalent ions
3+ 3+
Sc to Ga as a function of the number of d electrons. (Low spin ions
are indicated by solid circles).

The enthalpies of hydration of transition metal ions are measured at (actually

extrapolated to) infinite dilution, when only six water molecules enter the
coordination sphere of the metal ion and an octahedral aqua complex is
formed. So you see that the enthalpy of hydration and the enthalpy of
formation of the hexaaqua complex are having some relation. If you plot the
values of Hhyd for the +2 and +3 ions of the first transition elements (except
Sc2+, which is unstable) as a function of atomic number, then you get curves
much like those in Fig. 11.2. Similar patterns of a double-humped curve out of
the thermodynamic data for the coordination compounds are found following
the trends of variations in CFSE with d orbital configuration.

11.2.2 Ionic Radii

A slightly different form of the typical two-humped curve is shown by the ionic
radii of the 3d divalent metals. These are plotted in Fig. 11.2. In both Fig.
11.2a (dipositive) and Fig. 11.2b (tripositive) ions, the radius decreases for the
strong field case and this reaches a minimum at t 26g configuration. Here the
additional electron enters the eg level. Since the orbital is directed at the
ligands, the electron repels them and the effective radius of the metal
increases. For the same reason, in the case of high spin ions with the
t 23g e g1 configuration there is an increase in radius.

11.2.3 Thermodynamic and Related Aspects of

Crystal Fields
Now, you will study how the stability of a particular oxidation state of a
transition metal can be found with the help of crystal field theory. Co(III) is 33
Block 3 Crystal Field Theory and Its Applications

unstable in aqueous solution and get reduced by water to form Co(II). The
high third ionization energy of cobalt may be involved in this. The Co(III) ion is
perfectly stable if various moderate-to-strong field ligands are present in the
solution. The oxidation of Co(II) to Co(III) is definitely quite fast in some
cases.

For example, the appropriate emfs (in volts) are given in Eqs. 11.1-11.7:

[Co(H2O)6 ]2 [Co(H2O)6 ]3  e  E 0  1.83 …(11.1)

[Co(ox )3 ]4  [Co(ox )3 ]3   e  E 0  0.57 …(11.2)

[Co(phen)3 ]2  [Co(phen)3 ]3   e  E 0  0.42 …(11.3)

[Co( edta )]2  [Co(edta )]  e E 0  0.37 …(11.4)

[Co(en)3 ]2  [Co( en)3 ]3   e  E 0  0.18 …(11.5)

[Co(NH3 )6 ]2  [Co(NH3 )6 ]3   e  E 0  0.11 …(11.6)

[Co(CN)5 H2O]3  [Co(CN6 )]3   H2O  e  E 0  0.83 …(11.7)

These follow the order similar to the spectrochemical series that is same as
that of increasing crystal field stabilization energies. The oxidation in this case
is, the first being the rearrangement of electrons to the low spin state and the
second the removal of the eg electron to produce Co(III) as shown below:

Co2  (t 25g e1g )  Co 2  (t 26g eg1 )  Co3  (t 26g eg0 )

All this is considered to find out the clear thermodynamics as a result of some
steps. The first step has the electrons paired which requires energy. But
additional CFSE of the low spin configuration (1.8o versus 0.8o)
compensates for this. The magnitude of o increases as the strength of the
field increases. An electron from the eg level is removed in the second step
and the process has the high ionization energy (Co2+ to Co3+). So, it is
endothermic and the increase in CFSE (1.8o to 2.4o) favours ionization. So
you see that CFSE is only one of a number of factors affecting the EMF.
Chelate rings have different entropy effects associated with them. So in Eqs.
11.1-11.7 you can see a different order of ligands different from that in the
spectrochemical series. In biological systems, by varing the nature of the
ligands, the EMF of a couple is varied in similar way.

11.2.4 Heats of Ligations

Now we will study the enthalpy of hydration of transition metal ions. It is the
exchange involved when 1 mole of gaseous ions become hydrated

M(2g)  excess H2O [M(H2O)6 ]2 

The amount of energy released when a mole of the ion dissolves in a large
amount of water forming an infinite dilute solution in the process is the heat of
hydration. Higher the charge on the ions and smaller the size, more
34 exothermic will be the hydration energy. So it is expected to increase smoothly
Unit 11 Applications & Limitations of Crystal Field Theory

on going from left to right of the transition metals (green line in the graph) as
shown in Fig. 11.3.

Fig. 11.3: Heats of hydration for the transition elements

The heats of hydration show two “humps” consistent with the expected CFSE
for the metal ions. The value for d5 and d10 are the same as expected with a
CFSE equal to 0.

11.2.5 Site Preference Energies

Now let us see the case of site preferences in certain crystalline materials
such as the spinels. Spinels have the formula AB2O4, where A can be a Group
2 metal or a transition metal in the +2 oxidation state and B is a group 3 metal
or a transition metal in the +3 oxidation state. In one AB 2O4 unit, there are
eight tetrahedral holes and four octahedral holes where the oxide ions form a
close-packed cubic lattice. Normal spinels such as MgAl2O4 has one-eighth of
the tetrahedral holes occupied by the Mg2+ ions and the Al3+ ions occupy one-
half of the available octahedral holes. This gives a coordination number of 4
for the divalent ion and 6 for the trivalent ion (cf. [Be(H2O)4]2+ and [AlH2O4)3+).
Thus, it must be most stable. Spinels with inverse structure have the A(II) ions
exchanging place with one-half of the B(III) ions. So even intermediate cases
between the normal and inverse arrangements are seen. We can define
normal and inverse spinels with the help of a parameter . For normal spinels,
the value of  ranges from zero. It goes down to 0.50 for those having the
inverse composition. Cation distributions (as  values) in a number of common
spinels are given in Table 11.1.

Table 11.1: values of  for spinels, A IIBIII2O 4

3+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+
B /A Mg Mn Fe Co Ni Cu Zn

Al3+ 0 0 0 0 0.38 - 0
3+
Cr 0 0 0 0 0 0 0

Fe3+ 0.45 0.1 0.5 0.5 0.5 0.5 0

3+
Mn - 0 - - - - 0
3+
Co - - - 0 - - 0
(Source: J. E. Huheey, E. A. Keiter and R. L. Keiter, (1993), “Inorganic chemistry: Principles of
Structure and Reactivity”, fourth ed., HarperCollins College Publishers, New York) 35
Block 3 Crystal Field Theory and Its Applications

Fig. 11.4: Spinel.

In Fig. 11.4 is given the structure of a common spinel and Fig. 11.5 gives the
AB2O4 spinel.

Fig. 11.5: AB2O4 Spinel.

SAQ 1
Although Ni(acac)2 is paramagnetic, it is not tetrahedral. Suggest a structure
consistent with these facts.

11.3 LIMITATIONS OF CRYSTAL FIELD THEORY

In this section, we will discuss the limitations of the crystal field theory:

(1) It considers only the purely electrostatic forces between the ligand atoms
and the d electrons of the metal ion. The representation of the ligand is
not realistic. The covalent nature of the metal-ligand bond is also not
taken into consideration.

(2) The relative strength of ligands in the spectrochemical series is not

explained much by crystal field theory. There are no clear cut explanation

regarding why OH is a weaker ligand than H 2O. Neutral CO has very low
dipole moment ( = 0.11 debye) but still it is in the higher position of the
spectrochemical series. This is also not explained by this theory.

(3) Only the metal d orbitals are taken here. The ligand orbitals and the metal
s, px, py, pz orbitals are not considered at all. Also, the formation of a 
bond in a complex is not explained by this.

11.3.1 Molecular Orbital Theory

Molecular orbital theory has a totally different approach. The initial step is to
search for the correct symmetry and energies of the metal orbitals and the
36 ligand orbitals (hybridized) which combine to yield molecular orbitals. Next the
Unit 11 Applications & Limitations of Crystal Field Theory

electrons from the ligands and metal ion are placed into these molecular
orbitals. Thereafter the bond order, which is a measure of the covalency, is
determined. The energy sequence of molecular orbitals in the complex once
determined gives clues for the properties of the complex. So at the end the
bond type is understood. Although MOT is much more comprehensive than
the VBT or CFT, but people find it tedious to use. The applications of the
molecular orbital theory on coordination compounds match the experimental
observations even though it involves tedious quantum mechanical
calculations.

The second approach, though not as perfect, is more useful where the
calculations are based on crystal field theory. The differences between the
calculated values and the experimental results are taken into consideration as
the basis of covalency. This is known as adjusted crystal field theory or
even ‘ligand field theory’. Some authors prefer to call the molecular orbital
theory as ligand field theory, which is not actually correct.
The crystal field theory has a number of limitations which are noteworthy
eventhough it explains a number of data on transition metal complexes. The
assumption that the splitting of metal d orbitals is a result solely of electrostatic
effects and that the bond between metal and ligands is ionic with no covalent
character can be challenged by many experimental and semitheoretical
arguments.

11.3.2 Nephelauxetic Effect

In this section we are going to study evidences which indirectly comes from
the nephelauxetic effect to support sharing of electrons between the ligands
and the central metal ion. Electron-electron repulsion in complexes is found to
be a bit less than

Table 11.2: Crystal field data for aqua complexes of metal ions in the first
transition series
No. of d Ion Free Octahedral Tetrahedral o bt CFSE (kJ
1
Octahedral site
electrons ion field field 1 1 mol ) preference energy
cm cm
ground configuration configuration (kJ mol1)
Oct. Tetr.
state

1 Ti3  2
D 1
t 2g e1 20,100 8930 96.2 64.1 32.1

2 V3 3
F 2
t 2g e2 19,950 8870 190.9 127 64

3 V 2 4
F 3
t 2g e 2t 21 12,100 5380 174 51.5 122

Cr 3  4
F 3
t 2g e 2t 21 17,400 7730 250 74.0 176

4 Cr 2  5
D t 23g 31g e 2t 22 14,000 6220 101 29.8 71

Mn3  5
D t 23g e1g e 2t 22 21,000 9330 151 44.6 106

5 Mn2  6
S t 23g eg2 e 2t 23 7500 3330 0 0 0

F3  6
S t 23g eg2 e 3t 23 14,000 6220 0 0 0

37
Block 3 Crystal Field Theory and Its Applications

6 F2  5
D t 24g eg2 e 3t 23 9350 4160 44.7 29.9 14.8

Co3  5
D 6
t 2g e 3t 23 20,760 - - - -

7 Co 2  4
F t 25g eg2 e 4t 24 9200 4090 88.0 58.7 29.3

8 Ni2  3
F t 26g eg2 e 4t 24 8500 3780 122 36.2 86

9 Cu2  2
D t 26g eg3 e 4t 25 12,000 5330 86.1 25.5 60.6

that in the free ion. From data derived from electronic spectra of complexes,
we can find that when electron-electron repulsion decreases, nephelauxetic
effect increases (Table 11.3). Larger MOs formed from combination of metal
and ligand orbitals result in electronic repulsion. So an effective increase in the
distance between electrons deceases. (Nephelauxetic means “Cloud
expanding”). The ligands that are most effective in delocalizing metal electrons
display the largest values of the nephelauxetic parameter, h. So you see, the
softer the ligand, the smaller the nephelauxetic parameter. In other words, it
could be written as follows:

"Electron-electron repulsions are lesser in complexes than in free ions

because of the electron delocalization, the nephelauxetic parameter is a
measure of the extent of the d-electron delocalization onto the ligands of a
complex; the softer the ligand, the smaller the nephelauxetic parameter".

Table 11.3: The nephelauxetic series of ligands and metal ions

Ligand h Metal k Ligand h Metal k

F 0.8 Mn(II) 0.07 Cl 2.0 Rh(III) 0.28

H2O 1.0 V(II) 0.1 CN 2.1 Ir(III) 0.28

Urea 1.2 Ni(II) 0.12 Br 2.3 Co(III) 0.33

NH3 1.4 Mo(III) 0.15 N3 2.4 Pt(IV) 0.6

en 1.5 Cr(III) 0.20 I 2.7 Pd(IV) 0.7

ox 1.5 Fe(III) 0.24

(Source: J. E. Huheey, E. A. Keiter and R. L. Keiter, (1993), “Inorganic chemistry: Principles of

Structure and Reactivity”, fourth ed., HarperCollins College Publishers, New York)

Electron paramagnetic resonance (EPR) gives more evidences to justify

covalent character in metal-ligand bonds. Unpaired electrons behave like
magnets due to their spins. Thereby they align themselves either parallel or
antiparallel to an applied magnetic field. There is a bit of energy difference
between these two alignments. If the unpaired electron which do not undergo
interactions with other unpaired electrons or with magnetic nuclei, then it will
be undergoing a single absorption for this transition. But, the EPR spectra of
many complexes are seen in the regions of hyperfine splitting patterns that
arise from the interaction of the unpaired metal electron with magnetic nuclei
on the ligands. So it substantiates the fact that the electron is at least partially
38 delocalized over the ligands. This may be found out by EPR.
Unit 11 Applications & Limitations of Crystal Field Theory

SAQ 2
Give the octahedral as well as tetrahedral field electronic configuration for the
V2+ and Mn3+ ion. Which site will be preferred by these ions, octahedral or
tetrahedral? Justify your answer.

11.4 Pi-BONDING AND MOLECULAR ORBITAL

THEORY
Ligands not only form  bonds, some of them can even form  bonds with a
metal. Even though the correct symmetry is there for the ligand orbitals so
that they can participate in  bonding, for some ligands it does not take place
to much extent. The proper symmetry for  bond formation may exist in the
ligand and metal orbitals, but little or no interaction takes place due to a
mismatch of energy or size.

You must have studied that a nodal surface exists in the  bond which has the
bond axis. On each side of this nodal surface of the  bonding orbital lobes of
opposite sign exist. An octahedral complex could have up to twelve such
bonds--two between the metal and each of the six ligands from the standpoint
of orbital symmetry. But, this number does not exist in an actual complex.
Metal and ligand orbitals which take part in  bonds should be perpendicular to
the internuclear axes. So, the metal-ligand  interactions may be: (1) dp, (2)
dd, (3) d, and (4) d (Fig. 11.6). In Table 11.4 are given examples of
ligands capable of each type. In principle, either the ligand or the metal can
function as the electron donor. Both filled metal d orbitals can donate electron
density to an empty orbital on the ligand, as well as an empty d orbital on the
metal can receive electron density from a filled orbital of the ligand.

Look at different ligand group orbitals (Fig. 11.7) where t2g, t1u, and t1g are the
four symmetry categories in an octahedral complex of a transition metal. Only
two of them who can take part in interactions are the

Fig. 11.6: Pi overlap of a metal d orbital with various types of ligand orbitals: (a)
p, (b) d, (c) , and (d)  .

t2g (d xy , d xz , and d yz ) and t1u ( px , py , and pz ). The metal can form  bonds
with all of these orbitals. But, the members of the t1u set are directed towards
the ligands and so strong  bonds take place. If  bonds are used to form
these orbitals then the  system becomes weak and so it is favourable. But
the t2g orbitals are directed between the ligands and so in a -only system
(Fig. 11.7b), they have a nonbonding status. But they can very well bond to
LGOs of matching symmetry (Fig. 11.7). The t 2u and t1g ligand group orbitals 39
Block 3 Crystal Field Theory and Its Applications

are nonbonding in nature since the metal orbitals of matching symmetry are
not there. So you see pi bonding in an octahedral complex can happen with
the orbitals of t 2g symmetry.

Fig. 11.7: Overlap of ligand orbitals in the xy plane with (a) metal d and
x2  y 2
(b) dxy orbitals.

(Note that an appropriate choice of sign for the ligand orbitals provides positive
overlap with the d 2 2 orbital; however, no single sign choice for the ligand
x y

wave function produces positive overlap with the dxy orbital). One of the
simplest cases of  bonding in octahedral complexes is found in [CoF6 ]3  . In
Fig. 11.7 a similar  system is shown. The t2g orbitals of the metal can
interact with t2g LGOs constructed from the fluorine 2p orbitals to form
-bonding and antibonding molecular orbitals. Now, fluorine is more
electronegative than cobalt. In this case the fluorine 2p orbitals will be at a
lower energy than the corresponding metal 3d orbitals. In this case, the
bonding  MOs will resemble the fluorine orbitals more than the metal orbitals.
Thereafter the  MOs will more closely resemble the metal orbitals (as you
have studied earlier). The molecular orbital energy diagram for the system in
[CoF6 ]3  is shown in Fig. 11.7. Since the 2p orbitals on the fluoride ligands
are filled

Table 11.4: Pi bonding in coordination compounds

p  d Electrons from filled p orbitals of ligand are RO  ,RS  , O2  ,F ,

donated to empty d orbitals of metal
Cl ,Br  ,I ,R 2N

d  d Electrons from filled d orbitals of metal are R3P,R3 As,R2S

donated to empty d orbitals of ligand

d    Electrons from filled d orbitals of metal are CO, RNC, pyridine, CN ,
donated to empty  antibonding orbitals of
ligand N2 ,NO2 , ethylene

d    Electrons from filled d orbitals of metal are H2 ,R3P, alkanes

donated to empty  orbitals of ligand
40
Unit 11 Applications & Limitations of Crystal Field Theory

 Oh E 8C3 6C2 6C 4 3C2 (  C 42 ) i 6S 4 8S6 3 h 6 d

12 0 0 0 4 0 0 0 0 0
=

 = t1g + t2g + t1u + t 2u

Fig. 11.7: Identification of the symmetries of ligand group orbitals and metal
orbitals capable of participating in bonds (represented as vertices) in
an octahedral ML6 complex.

Note that the characters and irreducible components of the reducible

representation, , were derived by application of the same methods used for
the -only system, these electrons will fill the resultant molecular t 2g  orbitals.
Here, compared to the state where  bonding would not have taken place, the
electrons from the 3d (t 2g ) orbitals of the cobalt are at a higher energy, that is
in  antibonding orbitals (). But, eg orbitals do not have any change in their
levels due to  interaction.  bonding thus reduces the value of o. Fluoride
(and other halides) are at the weak field extreme in the spectrochemical series
(weaker than most -only ligands) and the reason for this may be this 
bonding. In the same way, that OH has a weaker field compared to H2O,
cannot be explained by purely electrostatic model. That hydroxide ion is a
better  donor may be the explanation for this. Note that the overall gain in
bond energy as a result of a  bonding is slight. t2g orbitals which are filled
are a bit lowered in energy, but t2g orbitals which are nearly filled are raised
an equal amount. So the crystal field stabilization energy is due to the slightly
different populations of the two sets of orbitals. Even oxyanions of transition
metals in high oxidation states such as CrO24 , MnO 24 and FeO24 may contain
 bonding. The  bonding in these cases may be thought of to exist between
metal and O2  ligand. But the tetrahedral complexes makes  bonding difficult
to happen.
Ligands such as R3P may participate in  bonding in similar lines as NH3. -
bond takes place from the ligating atom to the metal and it takes place through
an approximately sp3 hybrid orbital. But phosphorus has empty 3d and 
orbitals lying low enough in energy which is not there in nitrogen. So
phosphorus can easily receive electron density from the metal. The orbitals
thus formed have fairly low electronegativities in comparison to the metal
orbitals. The t 2g LGOs formed from them will therefore lie at a higher energy
compared to those of the corresponding metal orbitals. The resulting energy
level diagram is show in Fig. 11.8. Although the t2g orbital of the complex is
lowered and the t2g LGOs raised 41
Block 3 Crystal Field Theory and Its Applications

Fig. 11.8: Pi overlap of t2g LGOs with a metal t2g(dxy) orbital.

In Fig. 11.8 there are two additional sets perpendicular to the one shown.

3
Fig. 11.9: MO diagram for the  system of [CoF6) . Left: MOs for the  system
of the complex; right: LGOs of t2g symmetry: centre; MOs after
 interaction. Note that o is diminished by the  interaction.

in a manner similar to that of the previous case, here the t2g orbitals of the
ligand are empty. So the t2g orbitals may rise in energy with no cost of energy
and there is stabilization of the t2g orbitals. So an increase in the bond energy
can stabilize a complex by this sort of pi bonding. Also there is delocalization
of the resulting t 2 g  orbital over both metal and ligand which is not there in a
nonbonding t 2g orbital. In the latter case  bonding is absent. Electron
density is thus removed from the metal as a result of  bonding. But if there is
a metal in a high formal oxidation state in a complex, then this will not be
favoured as the metal already has a partial positive charge. But whenever the
oxidation state is low,  system gives rise to electron density which can go
from the metal to the ligand, and the metal is able to accept more via the 
system. Also, the ligand gets its electron density removed more by the 
system, and thereby the ligand can accept electron density readily through the
 system. Till certain point, each of these systems can help in the bonding
possibilities of the other.

But crystal field theory could not address the case of strong field ligands which
could be solved by the explanation of pi bonding betwen metal and ligands.
42 Let us now look at the strong field end of the spectrochemical series, where
Unit 11 Applications & Limitations of Crystal Field Theory

Fig. 11.10: MO diagram for the  system of an octahedral complex with acceptor
ligands such as CO, PR3 or SR2.

(Note that the  interaction in this case increases o as shown in Fig. 11.10)

Fig. 11.11: MO diagram for an octahedral M(CO)6 complex, both  and 

interactions are included.

(Correlation lines are drawn in Fig. 11.11 only to those molecular orbitals to
which the metal d electrons contribute.)

we find ligands such as nitrite ion, cyanide ion, carbon monoxide, phosphites,
and phosphines. The latter two owe their positions in the series to their ability
to serve as  acceptors, as described above, which increases the value of
o relative to what it would be in a -only system (Fig. 11.10). The other three
ligands  bond in a similar way. Only in their case the acceptor orbital is a 
orbital as shown in Fig. 11.10. Ligands in which either d or  orbitals or both
serve as  acceptors has the similar situation. They have such lowering of the
bonding t2g level that it raises the value of o to a great extent. In Fig. 11.11 is
shown a molecular orbital diagram for an octahedral M(CO)6 complex taking 43
Block 3 Crystal Field Theory and Its Applications

care of the  interactions.  bonding causes a good amount of increase in o .

So the absorption maximum for the t2g to eg electronic transition in many
such complexes is blue-shifted that is from the visible region it moves into the
ultraviolet region of the electromagnetic spectrum giving colorless complexes.
For example this is the case for the metal carbonyls,.

But it is not the same for halide ions such as Cl , Br  and I where similar to
fluoride ion filled p orbitals exist, even though their empty d orbitals take part in
 bonding (but in fluoride it does not). t2g LGOs constructed from filled p or
from empty d orbitals have a stronger interaction with the t2g orbitals of the
metal. It is found that all the halide ions are at the weak-field end of the
spectrochemical series, so we can say that the p-orbital interaction has a
greater importance than that of the d orbitals.

The potential for  orbitals to serve as  aceptors has become apparent in

recent times. Phosphines instead of using empty pure d orbitals as 
acceptors, may accept  donation into low-lying  orbitals or into hybrids
involving  and 3d orbitals. In addition, the coordination of dihydrogen is
thought to involve  electron donation to the metal from the HH  bond and
back donation from the metal into the H2  orbitals.

SAQ 3
The partial molecular orbital diagrams of Figs. 11.9 and 11.10 show that for
-donor ligands 0 is the energy separating between t2g and eg , while for
-acceptor ligands 0 is the energy separating between t 2g and eg . What is
the reason for the difference? As part of your answer to this question,
construct qualitative molecular orbital diagrams for [CoF6]3- and the
hypothetical [Co(PR3)6]3+; include all ,  and nonbonding electrons.

11.5 SUMMARY
In this unit we have discussed the applications of crystal field theory, in context
with lattice energies and ionic radii. Then we discussed the thermodynamic
aspects like heats of ligation and site preference energies. The limitations of
crystal field theory in context with m olecular orbital theory and nephelauxetic effect
along with pi-bonding and molecular orbital theory were dealt with also. In the
next unit we are going to learn about the basics of magnetochemistry.

11.6 TERMINAL QUESTIONS

1. What is the shape of the curve which shows the lattice energies of the
divalent metal halides of the 1st series. Also, give the reasons for
obtaining such a shape of the curve in the light of crystal field theory.

2. Of the twelve ions listed in Table 11.1, the only ones that consistently
form a large number of normal spinels are Zn2+ and Cr3+. Account for
44 these observations
Unit 11 Applications & Limitations of Crystal Field Theory

3. Regarding the drawbacks of the crystal field theory, Explain how it is does
not explain the relative strength of ligands in the spectrochemical series.

4. When coordination compounds form pi bonding then the ligans

R3P,R3 As,R2S would show what type of pi bonding and what would be the
reason of such bonding.

5. Give the molecular orbital diagram for an octahedral M(CO)6 complex.

11.7 ANSWERS
Self Assessment Questions
1. Nickel(II) has eight d electrons, if we pack them into the octahedral or
tetrahedral complex we will end up with two unpaired electrons. But if we
stick the electrons into a square planar complex then if the difference in
the energy between the two uppermost d orbitals in energy is sufficient
then we will get a low spin d8 complex. To get spin-pairing, the energy
difference between the orbitals must be greater than the energy required
to spin pair two electrons..

2. Table 11.2, V2+ is for d3 electrons and Mn3+ is for d4 electrons. They will
prefer the octahedral sides (section 11.3.2).

3. Figs. 11.9 and 11.10. Explanation is given section 11.4.

Terminal Questions
1 Fig. 11.1 (Section 11.2.1)

2 Spinels with inverse structure have the A(II) ions exchanging place with
one-half of the B(III) ions. So even intermediate cases between the
normal and inverse arrangements are seen. We can define normal and
inverse spinels with the help of a parameter . For normal spinels, the
value of  ranges from zero. It goes down to 0.50 for those having the
inverse composition. Cation distributions (as à values) in a number of
common spinels are given in Table 11.1

3 Section 11.3
4 d   d  , electrons from filled d orbitals of metal are donated to empty d orbitals
of ligand

5 Fig. 11.11

FURTHER READING
1. J. E. Huheey, E. A. Keiter and R. L. Keiter, (1993), “Inorganic chemistry:
Principles of Structure and Reactivity”, fourth ed., HarperCollins College
Publishers, New York.

2. Mark Weller, Fraser Armstrong, Jonathan Rourke & Tina Overton

(Formerly D. F. Shriver, P. W. Atkins and C. H. Langford, Inorganic
chemistry, 6th edition, Oxford University Press, India.
3. https://web.iitd.ac.in/~sdeep/Elias_Inorg_lec_2.pdf
45