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CHAPTER 3 STRUCTURES OF METAL COMPLEXES

3.1 Introduction..1
3.2 Genera C!aracteri"tic" o# Coordination Co$%ound"..... 2
3.2.1 Coordination Compounds2
3.2.2 Lewis Structures and the EAN Rule3
3.2.3 Types o Li!and Coordination. "
3.2." Types o Li!ands..
#
3.3 Moecuar Or&ita and Cr'"ta Fied T!eorie"..$
3.3.1 %olecular &r'itals o %etal(Li!and Comple)es. $
3.3.2 Li!and *ield Splittin! and the Spectrochemical Series. 1+
3.3.3 Crystal *ield Theory.. 11
3.3." Electron Coni!urations. 12
3.3.# Crystal *ield Sta'ili,ation Ener!y. 1-
3.( Hard and So#t Acid" and )a"e"1.
_____________________________________________________________________________
_
3.1 Introduction
In general, a metal ion exists in compounds and in aqueous solution, not as a naked ion, but
as an aggregated entity consisting typically of a central metal ion bound to a certain number of
anions or molecules. This entity is called a complex or coordination compound, and the bound
anions and molecules are termed ligands . The ligands occupy the coordination sphere of the
central metal ion and the number of bound ions and molecules associated with a given central ion
represents the coordination number of the metal ion. The metal complex may be neutral, anionic
or cationic, depending on the combination of charges on the central metal ion and the ligands.
Complexing ligands are exploited in several aqueous-based unit processes, such as dissolution,
chemical precipitation, electrodeposition, solvent extraction, ion-exchange, and adsorption.
This chapter deals with the structures of metal-ligand complexes, with emphasis on transition
metals. We begin by considering how we can understand the structures of coordination
compounds through the Lewis concept of the electron-pair bond. We then examine how
molecular orbital theory can be extended to metal-ligand complexes. Finally, some useful
generalizations are presented which should aid in the selection of ligands for specific metal ions.
3.2 General Characteristics of Coordination Compounds
3.2.1 Coordination Compounds
The serious study of coordination compounds did not begin till the end of the 18th century.
At this time the available theory of chemical bonding could not explain why compounds such as
CoCl
3
and NH
3
, with apparently saturated valences, would combine to give a new stable
compound with stoichiometry CoC1
3
6NH
3
. Hence such compounds were termed complex,
recognition of their unknown and apparently baffling bonding mechanism. It is now recognized
that the structural chemistry of a complex is based in part on two key properties of the central
metal ion, i.e., its oxidation state, and its coordination number. Thus, in the case of
CoCl
3
6NH
3,
the structural formula may be expressed as [Co(NH
3
)
6
]Cl
3
, with the following
interpretation. The oxidation state of cobalt in this complex is +3 (i.e., Co(III)) and hence three
negatively charged chloride ions are needed to satisfy this charge. On the other hand, the
ammonia molecules provide the necessary ligands to satisfy the coordination number of six; that
is, these molecules are bound directly to the metal ion.
The unique character of coordination compounds often manifests itself in the different
solution behavior of stoichiometrically similar compounds. Take for example the two
compounds with the similar stoichiometric formulas: 2KClHgCl
2
and 2KClMgCl
2
. These two
materials dissolve in water differently:
2KClHgCl
2
= 2K
+
+ HgCl
4
2-
(3.1)
2KClMgCl
2
= 2K
+
+ Mg
2+
+ 4Cl
-
(3.2)
The first compound, 2KClHgCl
2
, is a coordination compound since the chloride ions are not
released as free ions into the aqueous phase but rather are retained in the coordination sphere of
the Hg
2+
cation. Accordingly, to emphasize the intimate association of the chloride and
mercuric ions, the structural formula for this compound may be expressed as K
2
[HgCl
4
]. On the
other hand in the case of the second compound, all the chloride ions report as free ions into the
aqueous phase. Therefore this compound is a double salt (rather than a coordination compound)
and its structural formula can be legitimately expressed as 2KClMgCl
2
.
______________________________________________
EXAMPLE 3.1 Identification of bound and free chloride ions in cobaltic ammine chloride solutions
Cobaltic ammine chlorides have the general stoichiometric formula CoCl
3
nNH
3
. In these coordination
compounds cobalt has an oxidation state of +3 and a coordination number of 6. Also, of the potential ligands NH
3
and Cl
-
, ammonia molecules are bound preferentially to cobalt ions.
(a) Write down the structural formulas of the following complexes: (i) CoCl
3
6NH
3
, (ii) CoCl
3
5NH
3
,
(iii) CoCl
3
4NH
3
.
(b) When a solution of silver nitrate is added to a solution of CoCl
3
nNH
3
, the silver ions react with the
unbound chloride ions to give an insoluble precipitate of silver chloride (AgCl(s)). For each of the
complexes listed above, indicate the number of chloride ions precipitated.
Solution
(a) According to the problem statement, all the available NH
3
will first bind to Co
3+
before Cl
-
can enter the
coordination sphere. Therefore, since Co
3+
has a coordination number of 6, the coordination sphere of
Co
3+
in CoCl
3
6NH
3
. will consist entirely of NH
3

molecules. Thus, there will be three unbound Cl
-
ions.
Therefore, the coordination formula is [Co(NH
3
)
6
]Cl
3
. Similar considerations result in appropriate
coordination formulas for the other cobaltic ammine chloride complexes, as summarized in the table below.
(b) Since the silver ion will only react with the unbound chloride ions, it is necessary to identify the number of
free chloride ions associated with each cobaltic ammine chloride. The results of the analysis are
summarized in the table below.
Molecular No. of No. of Coordination No. of Cl
-
ions
Formula Bound NH
3
Bound Cl
-
Formula Precipitated
_____________________________________________
CoCl
3
6NH
3
6 0 [Co(NH
3
)
6
]Cl
3
3
CoCl
3
5NH
3
5 1 [Co(NH
3
)
5
Cl]Cl
2
2
CoCl
3
4NH
3
4 2 [Co(NH
3
)
4
Cl
2
]Cl 1
_____________________________________
3.2.2 Lewis Structures and the EAN Rule
Comparison of the Lewis diagrams obtained in Chapter 2 for NH
3
and H
2
O shows that
NH
3
possesses an unshared electron pair, while in the case of H
2
O there are two pairs of
unshared electrons. These lone electron pairs can be shared in the formation of new compounds.
Thus an ammonium (NH
4
+
) ion forms when the electron pair on NH
3
is shared with a hydrogen
ion:
H
+
+ :NH
3
= [H3N: H]
+
= NH4
+
(3.3)
Similarly, the oxonium ion (H
3
O
+
) results when a water molecule shares one of its two lone
electron pairs with a proton:
H
+
+ :OH
2
= [H
2
O: H]
+
= H
3
O
+
(3.4)
Equations 3.3 and 3.4 represent Lewis acid-base reactions. According to the Lewis
theory of acids and bases, an acid is a substance that can accept an electron pair, whereas a base
is a substance that can donate an electron pair. According to this terminology, one may refer to
an acid as an acceptor and a base as a donor. Thus, the formation of a complex or a coordination
compound can be viewed in terms of an acid-base reaction:
A + :B = B: A (3.5)
(Acid; acceptor) (Base; donor) (Complex)
In the case of metal complexes, the metal ions represent the acids while the ligands represent the
bases. Thus the formation of the cobaltic hexammine complex can be represented as:
(3.6)
It will be noticed that for He (Z = 2), Ne (Z = 10), and Ar (Z = 18), the atomic numbers
change in increments of 8. In contrast, for Ar (Z = 10), Kr (Z = 36), and Xe (Z = 54), the
corresponding increment is 18. This difference translates to a modification of the Lewis eight-
electron rule to an Effective Atomic Number (EAN) rule for transition metal complexes.
According to the EAN rule, the ligands in the coordination sphere of a transition metal complex
must provide the necessary number of electrons that will give the central metal ion the electronic
configuration of a rare gas.
_____________________________________________________________________________
_
EXAMPLE 3.2 The EAN rule and the structure of Co(III) hexammine
Is the coordination of Co(NH
3
)
6
3+
consistent with the EAN rule?
Solution
The atomic number of Co is 27. Thus 24 electrons are associated with the Co(III) ion. Each NH
3
ligand can
offer a lone-pair, i.e., a total of 12 electrons from six ligand molecules. Therefore in the hexammine complex, the
Co(III) ion has a total of 36 electrons. This matches the electronic structure of Kr.
Alternatively, we recall from Table 2.2 that the electronic structure of Co is [Ar] 3d
7
4s
2
. Thus Co(III) has 6 valence
electrons. If we now add the 12 electrons provided by the ligands, we get a total of 18 electrons in the valence shell
of Co(III) in the complex. Thus we see that the EAN rule can be viewed, in this case, as an 18-electron rule.
____________________________________________________________________________________________
Co
3/
/ 0N1
3
2
1
3
N
N1
3
N1
3
N1
3
1
3
N
1
3
N

Co
3/
3.2.3 Types of Ligands
For most ligands the coordinating atom of the anion or molecule (i.e., the atom of the
ligand that is directly bound to the central metal ion) comes from Groups V, VI, or VII of the
Periodic Table, particularly N, P for groups V; O, S for group VI; and F, Cl, Br, I for group VII.
Table 3.1 presents a collection of common ligands and ligand atoms. We can distinguish
between monodentate ligands, characterized by the presence of only one binding site, and
polydentate ligands, which carry two or more binding sites. Examples of monodentate ligands
are cyanide (CN
-
), halide (F
-
, Cl
-
, Br
-
, I
-
), and ammonia (NH
3
). Bidentate ligands include
ethylene diamine, and acetylacetonate. Some polydentate ligands have binding atoms consisting
of different elements, e.g., glycinate (N, O), ethylenediaminetetracetate (EDTA; N,O).
In Table 3.1, certain ligands are associated with more than one ligand atom. Thus NO
2
-
appears under both nitrogen (N) and oxygen (O), SCN
-
is grouped with nitrogen (N) ligands as
well as with sulfur (S) ligands, both SO
3
2-
and S
2
O
3
2-
appear with the oxygen (O) and sulfur (S)
ligands. Ions or molecules which possess alternative donor atoms are given the name
ambidentate.
3.2.4 Types of Ligand Coordination
The coordination numbers encountered in metal complexes range from 2 to 9, the most
common being 6. There is only a limited number of complex ions with a coordination number of
2, and these are typically found among Group IB M(I) and Hg(II) complexes. The geometrical
arrangement of these complexes tends to be linear. In general, these bis complexes readily
accept additional ligands to give complexes with higher coordination. Three coordination in
metal complexes is also unusual. Thus, attempts to deduce three-coordination from
stoichiometry can be misleading. Thus, the 3-coordinate complex CuCl
3
-
does not exist in the
compound CsCuCl
3
. In fact, in this compound, Cu(II) has a coordination number of 4.
Similarly, in KCuCl
3
, the coordination number of Cu(II) is 6 not 3.
Two different coordination polyhedra are associated with a coordination number of 4, i.e.,
tetrahedral and square planar structures. The tendency towards the formation of a tetrahedral
structure can be rationalized in terms of steric constraints. That is, as ligands increase in charge
and/or size, there is a need for the ligands to be as far away from each other as possible. Due to
steric constraints, square planar structures are not favored by relatively large ligands. Relatively
small ligands do not favor square structures either; the ligands may be so small that two-
additional ligands may be readily accommodated below and above the square plane, giving an
octahedral complex. Thus, only a select group of metal ions can form square planar complexes.
Complexes with a coordination number of 5 are few. As with coordination number 3,
many complexes which appear from stoichiometry to be 5-coordinate may not have this
coordination at all. Examples of 5-coordination polyhedra are the trigonal bypyramid, and the
square pyramid. The coordination number 6 is the most common.
Table 3.1 Common Ligands and Ligand Atoms
Ligand Atom Common Ligands
Carbon (C) CN
-
Nitrogen (N) NH
3
, NO, SCN
-
, RNH
2
, R
2
NH, R
3
N
O
RC (Amide), RN=O (Nitroso),
NH
2
RC = N - OH (Oxime)
Oxygen (O) H
2
O, OH
-
, O
2-
, NO

2
, NO, CO, PO,
S
2
O, SO, SO, ClO, R-O-R (ether),
R-OH (Alcohol), RC=O (Ketone),
O
R - O O (Alkyl phosphate), RC OH (Carboxylate)
P
HO O
-
Sulfur (S) HS
-
, S
2-
, SO, S
2
O, SCN
-
, R-S-R- (Thioether),
R-SH (Mercaptan), R-S
-
,
O S
RC (Monothiocarboxylate), RC (Dithiocarboxylate)
S
-
S
-
R S
N C (Dialkyl dithiocarbamate)
R S
-
R O S
P (Dialkyl dithiophosphate)
R O S
-
H
2
N
C = S
-
(Thiourea)
H
2
N
Halogen (F, Cl, Br, I) F
-
, Cl
-
, Br
-
, I
-

Table 3.2 Coordination numbers of metal complexes.
Coord. No. Typical Examples
2 Group IB M(I) complexes, e.g.
M(NH
3
)
2
+
, where M(I) = Cu
+
, Ag
+
MCl
2
-
, where M(I) = Cu
+
, Ag
+
, Au
+
M(CN)
2
-
, where M(I) = Ag
+
, Au
+
Hg(II) complexes, eg., Hg(CN)
2
3
KCu(CN)
2
chain, [-CN-Cu(CN)-CN-Cu(CN)-CN-]
Triiodomercurate (II) anion, Hg I
3
-
4 (Square)
d
8
metal ions (e.g., Ni
2+
, Pd
2+
, Pt
2+
, Au
3+
)
4(Tetrahedral)
Large ligands (e.g., Cl
-
, Br
-
, I
-
) bonded to
(a) small metal ions with noble gas configuration,
ns
2
np
6
, e.g., Be
2+
(b) metal ions with pseudo-noble gas configuration,
ns
2
np
6
and (n-1)d
10
, e.g. Zn
2+
, Ga
3+
.
(c) transition metal ions which, for energetic reasons,
have no strong preference for other structures, e.g.,
Co
2+
(d
7
)
5
Pentachlorocuprate (III) anion, CuCl
5
3-
Pentacyanonickelate (III) anion, Ni(CN)
5
3-
6 Most Cr (III) and Co(III) complexes
7
8 Relatively small ligands (e.g., with C, N, O, F as
ligating atoms) bonded to relatively large metal cations
with high oxidation state: lanthanides, actinides, Zr, Hf, Nb, Ta,
Mo, W
9
Ln(H
2
O)
9
3+,
, Ln = early lanthanide metal
_____________________________ ______________________________________________
3.3 Molecular Orbital and Crystal Field Theories
3.3.1 Molecular Orbitals of Metal-Ligand Complexes
As discussed previously above (Section 2.5), we can view the formation of molecules as the
interaction between the valence orbitals of the constituent atoms. We shall now extend this
concept to metal-ligand complexes. Let us consider a d-metal atom, M, which forms a complex
ML
n
with six molecules of the ligand L. Nine atomic valence orbitals are available on the metal:
one s, three p, and five d. Suppose each ligand provides a single s-type atomic orbital, then for
the complex ML
n
, there will be (9+n) atomic orbitals in all. Corresponding to the n metal-ligand
bonds are n bonding and n antibonding orbitals. This leaves (9-n) orbitals, which then constitute
the nonbonding orbitals. The energy levels will be expected to increase in the order, bonding <
nonbonding < antibonding.
Figures 3.1, 3.2, and 3.3 present schematic diagrams which illustrate the molecular orbital
energy level schemes for octahedral, tetrahedral, and square planar complexes, respectively.
Figure 3.1 Energy level diagram for a sigma-bonded octahedral complex (Huheey, p.417).
Figure 3.2 Energy level diagram for a sigma-bonded tetrahedral complex (Huheey).
Figure 3.3 Energy level diagram for a sigma-bonded square planar complex (Huheey).
Application of molecular orbital theory to octahedral complexes requires the construction of
seven-centered molecular orbitals. In the case of both tetrahedral and square-planar complexes,
five-centered molecular orbitals are involved. It must be noted that the linear combination of
atomic orbitals is feasible only if the metal and ligand orbitals have the same symmetry.
The subscripts g (gerard), and u (even, ungerard) were encountered previously above. The
following additional labels are useful in describing the symmetry properties of metal-ligand
complexes. The subscript 1 indicates that the orbital does not undergo a sign change when
rotated about the Cartesian axes. The subscript 2 is used to indicate that there is no sign change
when the axis of rotation is diagonal to the Cartesian axes. For a particular energy level, the
labels a, e, and t respectively signify that, there is a single orbital, a set of two orbitals, and a set
of three orbitals. Thus the appropriate symmetry labels for the d-metal atomic orbitals are: a
1g
for s, t
1u
for p
x
, p
y
, p
z
, t
2g
for d
xy
, d
yz
, d
zx
, and e
g
for d
x
2-
y
2, d
z
2.
It is generally the case, as shown in the above diagrams, that the ligand energy level is lower
than the metal energy levels. The implication is that the bonding molecular orbitals tend to be
ligand-like in character.
3.3.2 Ligand Field Splitting and the Spectrochemical Series
It can be seen from Figures 3.1 and 3.2 that one outcome of the presence of ligands around
the central metal ion is that the five d-type molecular orbitals are split into two groups, separated
by an energy gap identified as
o
for octahedral coordination and as
t
for tetrahedral structures.
This effect is termed ligand field splitting. In the case of the square-planar energy level
diagram...
Ligands differ in the extent to which their orbitals interact with metal orbitals. A ligand
whose orbitals interact strongly with metal orbitals is termed a strong-field ligand. Such a ligand
will produce a large ligand field splitting. On the other hand, a weak-field ligand interacts
weakly and the resulting ligand field splitting is small. Table 3.3 presents ligand field splitting
data for selected octahedral complexes (Table 7.4 SAL, p.211). It can be seen that
o
varies with
both the metal and ligand. An empirically determined order of ligand fields, termed a
spectrochemical series, has been established for both ligands and metals. In the case of ligands,
the order is as follows:
I
-
< Br
-
< S
2-
< SCN
-
< Cl
-
< NO
3
-
< F
-
< C
2
O
4
2-
< H
2
O < NCS
-
<
CH
3
CN < NH
3
< en < bipy < phen < NO
2
-
< PPh
3
< CN
-
< CO
In cases where there may be some ambiguity, the binding site on the ligand is underlined. For
metal ions, the following order has been established:
Mn
2+
< V
2+
< Co
2+
< Fe
2+
< Ni
2+
< Fe
3+
< Co
3+
< Mn
4+
<
Mo
3+
< Rh
3+
< Ru
3+
< Pd
4+
< Ir
3+
< Pt
4+
(SAL, p.212).
Table 3.3 Ligand field splittings (
o
) of ML
6
complexes*
Ions Ligands
Cl
-
H
2
O NH
3
en CN
-

d
3
Cr
3+
13.7 17.4 21.5 21.9 26.6
d
2
Mn
2+
7.5 8.5 10.1 30
d
5
Fe
3+
11.0 14.3 (35)
d
6
Fe
2+
10.4 (32.8)
d
6
Co
3+
(20.7) (22.9) (23.2) (34.8)
d
6
Rh
3+
(20.4) (27.0) (34.0) (34.6) (45.5)
d
8
Ni
2+
7.5 8.5 10.8 11.5

*"Values are in multiples of 1000 cm
-1
; entries in parentheses are for low spin complexes."
"Source: H. B. Gray, Electrons and Chemical Bonding, Benjamin, Menlo Park (1965)."
(SAL, P.211)
The empirical trends exemplified by the spectrochemical series can be rationalized with the
aid of molecular orbital theory. Three important factors are: (a) the relative energies of the
metal and ligand orbitals, (b) the degree of overlap between metal and ligand orbitals, and (c) the
extent of metal-ligand pi bonding.
_____________________________________________________________________________
_
EXAMPLE 3.3 Metal - ligand combinations giving strong-field and weak-field complexes
Speculate on whether the following metal-ligand combinations are most likely to give weak-field or strong-field
complexes.
Solution
____________________________________________________________________________________________
3.3.3 Crystal Field Theory
It was noted above that one outcome of the presence of ligands around the central metal ion
is the splitting of the d-type orbitals into two main groups. Crystal field theory (CFT) focuses on
this characteristic feature of the energy level diagram. In the CFT approach to bonding in metal-
ligand complexes, the development of the energy gap is viewed electrostatically: A metal
complex is considered as consisting of a central metal ion embedded in a cluster of the negative
ions and molecular dipoles which constitute the ligands. The bonding between the central metal
ion and the surrounding ligands is attributed to electrostatic interaction arising from the electric
field of the metal ion and that of the ligands. The electrostatic field emanating from the negative
charges and the negative ends of the dipoles will tend to repel the outer electrons, particularly,
the d electrons of the central metal ion. That is, the greater the proximity of a ligand to a metal
orbital, the harder it is for an electron to occupy that orbital. A consequence of this repulsion is
an increase in the energy of the d-orbitals of the central ion.
As would be expected, the geometrical arrangement (e.g., octahedral, tetrahedral, square-
planar) of the ligands around the central ion has a significant influence on the electrostatic field
experienced by the central metal ion. Let us consider an octahedral complex. We envision the
six ligand ions or molecules to be distributed along the x, y, z Cartesian axes as illustrated in
Figure 3.4a. It can be seen that the ligand-metal orbital interactions will be greatest for the d
x
2-
y
2
and d
z
2
orbitals (i.e., the e
g
group) since these lie along the x, y, z axes. In contrast, there is a
smaller interaction with the d
xy
, d
xz
and d
yz
orbitals (i.e., the t
2g
group) since these lie in
between the ligands. Accordingly the e
g
orbitals acquire a greater energy than the t
2g
orbitals.
In the language of crystal field theory, this effect is termed crystal field splitting; it corresponds
to the ligand field splitting encountered previously above. Crystal field splitting for an
octahedral complex is illustrated in Figure 3.4b; the difference in energy between the e
g
and t
2g
orbitals is denoted as
o
. If one considers the energy of a hypothetical complex with degenerate
d orbitals (i.e. orbitals with the same energy), then it can be demonstrated that the e
g
and t
2g
orbitals are respectively 0.6
o
and 0.4
o
above and below this hypothetical energy level. A
similar analysis can also be performed for other ligand geometries, e.g., tetrahedral, and planar.
For tetrahedral complexes the ligand field effect causes a splitting of the d sublevel with the t
2g
orbitals lying above the e
g
orbitals. In general the crystal field splitting of the tetrahedral
arrangement (
t
) is about a half of the corresponding octahedral value (
o
).
(a) Metal-ligand orbital interactions





0.6


0.4
d
xy
d
xz
d
yz
d
x - y
2
2
d
z
2
e
g
{ }
t
2g
{ }
E
Metal ion
in absence
of ligand
Metal ion
bonded to
ligand in
hogeneous
field (dege-
nerate orbitals)
(b) (c) (d)
Metal ion bonded
to ligand: crystal
field splitting
Figure 3.4. Crystal field splitting for an octahedral complex
3.3.4 Electron Configurations
A major factor in working out the electron distribution in a metal-ligand complex, is the energy
level difference, . Let us return to the molecular orbital energy level diagram for octahedral
complexes shown in Figure 3.1. Each of the six ligand atoms supplies a lone pair of electrons.
The resulting twelve electrons fill up the six bonding orbitals. There can be a maximum of ten d
electrons; therefore, five orbitals are needed and these must be the next lower-lying orbitals, i.e.,
the t
2g
and e
g
* orbitals. The order in which the t
2g
and e
g
orbitals are filled by electrons, and the
extent to which electron pairing occurs, are both the combined effects of the energy level
difference
o
, the electrostatic energy (E
el
), and the exchange energy (E
ex
). We recall from
Section 2.2.4 that the total energy of a given electronic configuration (E
config
) is given by:
E
config
= E
elt
+ E
ext
(3.7)
where E
elt
is the total electrostatic energy associated with P
el
electron pairs and E
ext
(= P
ex
E
ex
)
is the total energy due to P
ex
parralel-spin electrons. For the condition
o
> E
config
, the leading
principle is that based on energy levels, and it is energetically more favorable to first fill up the
lower energy levels. On the other hand, when
o
< E
config
, the leading principle is the constraint
on electron pairing and the electronic configuration is more stable with unpaired electrons.
Table 3.4 Effect of the ligand field on the electron distribution in octahedral complexes


System Weak Field (High Spin) Strong Field (Low Spin)
t
2g
e
g
t
2g
e
g


d
0

d
1

d
2

d
3

d
4

d
5

d
6

d
7

d
8

d
9

d
10


The crystal field splitting can lead to modifications in the electron distributions in the five d
orbitals. As noted previously, Hund's rules require that all the d orbitals be occupied singly
before electron pairing begins, however, if the ligand field splitting is relatively large, then the e
g
orbitals will be significantly higher in energy than the t
2g
orbitals. Under these circumstances
the lower t
2g
orbitals will become completely filled before occupation of the higher e
g
orbitals
begins. Table 3.4 illustrates the different electron distributions for low and high ligand fields in
an octahedral complex. It can be seen that the d
4
, d
5
, d
6
, and d
7
systems differ significantly in
electron distribution, depending on whether they are subjected to a weak or a strong ligand field.
The presence of a weak field does not significantly influence electron pairing, and high-spin
complexes are said to form. On the other hand a strong field causes significant electron pairing,
and the resulting complexes are termed low-spin complexes.
____________________________________________________________________________________________
EXAMPLE 3.4 Effect of ligand field strength on the filling of d-orbitals
For a given central metal ion M
z+
, determine the tendency with which the following ligands may form low-spin
complexes: F
-
, phenanthroline, aliphatic amine, CN
-
, H
2
O.
Solution
The relative strengths of the ligand fields are given by the spectrochemical series. That is, the ligand field strength
increases in the order: F
-
< H
2
O < amine < phenanthroline < CN
-
. The stronger the ligand field, the greater the
tendency towards ion-pairing, and therefore the tendency to form low-spin complexes. Thus, low-spin complexes
are expected to form in the same order as the spectrochemical series, i.e., CN
-
complexes are likely to be low-spin
and F
-
complexes high-spin.

EXAMPLE 3.5 Magnetic moments and the structure of metal complexes
The magnetic moment (m
M
) of a metal complex is a reflection of the number of unpaired electrons (n) that the
central metal ion contains, i.e. m
M
= (n(n+2))
1/2
magnetons (1 Bohr magneton = 9.18 x 10
-21
gauss-cm/atom or
5564 gauss-cm/mol).
(a) Determine the magnetic moment (in Bohr magnetons) that corresponds to the following numbers of unpaired
electrons 0, 1, 2, 3, 4, 5.
(b) Determine the magnetic moment (in Bohr magnetons) of a free Fe
3+
ion.
(c) Given the following magnetic moments (shown in brackets), determine the corresponding number of unpaired
electrons for the central metal ion: (i) Fe(CN)
3
0
32.34, (ii) FeF
3
0
30.+4, (iii) Fe(CN)
"
0
(0).
Solution
(a) Given that m
M
= (n(n + 2))
1/2
magnetons, it follows that: (i) for n = 0, m
M
= 0; (ii) n = 1, m
M
= (1(1 + 2))
1/2
= 1.73; (iii) n = 2, m
M
= (2(2 + 2))
1/2
= 2.83; (iv) n = 3, m
M
= (3(3 + 2))
1/2
= 3.87; (v) n = 4, m
M
= (4(4 + 2))
1/2
= 4.90; (vi) n = 5, m
M
= (5(5 + 2))
1/2
= 5.92.
(b) Fe has the electronic structure [Ar] 3d
6
4s
2
. The corresponding structure of Fe
3+
is [Ar] 3d
5
4s
0
. The free Fe
3+
ion is situated in a weak field and therefore this ion has five unpaired electrons (see Table 3.4). Thus, it follows
from part (a) that m
M
= 5.92 magnetons.
(c) (i) Fe(CN)
3
0
, m
M
= 2.3 magnetons. From part (a), for n = 1, m
M
= 1.73 magnetons; this suggests that Fe(CN)
3
0
has one unpaired electron.
(ii) FeF
3
0
, m
M
= 6.0 magnetons. This suggests a structure with five unpaired electrons.
(iii) Fe(CN)
"
0
, m
M
= 0 magnetons. In this case there are no unpaired electrons.

EXAMPLE 3.6 Exchangeable electron pairs in high and low spin complexes
(a) Determine the number of exchangeable pairs for high spin and low spin complexes of (i) a d
6
ion, (ii) a d
5
ion.
(b) For both ions, determine the value of E
config
.
Solution
(a) (i) d
6
(high spin): The relevant electronic configuration is: . Thus, 5 spin down electrons
(i.e., N = 5) and 1 spin up electron (N = 1). Thus, the number of exchangeable pairs is given by
(Equation 2.2):
P
ex
() = N(N-1)/2 = 5(4)/2 = 10
P
ex
() = N(N-1)/2 = 1(0)/2 = 0
Thus the total number of exchangeable pairs is
P
ex
= P
ex
() + P
ex
() = 10 + 0 = 10
d
6
(low spin ): The electronic configuration is: . Accordingly, N() = 3, N() = 3.
Thus,
P
ex
() = P
ex
() = N(N-1)/2 = 3(2)/2 = 3
and,
P
ex
= P
ex
() + P
ex
() = 3 + 3 = 6.
(ii) d
5
(high spin) : The electronic configuration is: . Therefore, N() = 5, N( ) = 0. Thus,
P
ex
= P
ex
() = N(N-1)/2 = 5(4)/2) = 10.
d
5
(low spin): __ __. There are 3 spin-down electrons (N()=3) and two spin-up electrons
(N() = 2). Thus,
P
ex
= [3(3-1)/2] + [2(2-1)/2] = 3+1 = 4.

EXAMPLE 3.7 Spin configuration of aquo complexes
Presented below are orbital splitting (
o
) and mean pairing energy (E
pair
) data for aquo ions (cm
-1
). On the
basis of these data, speculate on the likelihood of the formation of low spin configurations.
Ion
o
E
pair
Ion
o
E
pair
d
1
Ti
3+
20,300
d
2
V
3+
18,000
d
1
Ti
3+
20,300
Solution
____________________________________________________________________________________________
3.3.5 Crystal Field Stabilization Energy
The amount of energy by which d orbitals are lowered in comparison with the hypothetical
undisturbed d orbitals is designated the crystal field stabilization energy (CFSE) of the complex.
Referring to Figure 3.4b, let us assign the zero of energy to the degenerate d levels in the
hypothetical homogeneous ligand field. Then, the energy of the e
g
orbitals is 0.6 , while that of
the t
2g
orbitals is -0.4
o
. Thus, for a given electronic configuration t
2g
a
e
g
b
, the net energy
relative to the degenerate levels, i.e., the crystal field stabilization energy (CFSE), is defined as:
CFSE = -(0.4a + 0.6b)
o
= 0.4a - 0.6b) (3.8)
Table 3.5 presents crystal field stabilization energies (in units of
o
) for octahedral, tetrahedral,
and square complexes.
Table 3.5 Crystal field stabilization energies for octahedral, tetrahedral, and square
complexes (in units of
o
).

Weak Field (High Spin) Strong Field (Low Spin)
System Examples Oct. Tet. Square Oct. Tet. Square
d
0
Ca
2+
, Sc
3+
0 0 0 0 0 0
d
1
Ti
3+
U
4+
0.4 0.27 0.51 0.4 0.27 0.57
d
2
Ti
2+
,V
3+
0.8 0.54 1.02 0.8 0.54 1.02
d
3
V
2+
, Cr
3+
1.2 0.36 1.45 1.2 0.81 1.45
d
4
Cr
2+
,Mn
3+
0.6 0.18 1.22 1.6 1.08 1.96
d
5
Mn
2+
,Fe
3+
,Os
3+
0 0 0 2.0 0.90 2.47
d
6
Fe
2+
,Co
3+
,Ir
3+
0.4 0.27 0.51 2.4 0.72 2.90
d
7
Co
2+
,Ni
3+
,Rh
2+
0.8 0.54 1.02 1.8 0.54 2.67
d
8
Ni
2+
,Pd
2+
,Pt
2+
,Au
3+
1.2 0.36 1.45 1.2 0.36 2.44
d
9
Cu
2+
,Ag
2+
0.6 0.18 1.22 0.6 0.18 1.22
d
10
Cu
+
,Zn
2+
,Cd
2+,
0 0 0 0 0 0
Ag
+
,Hg
2+
,Ga
3+

EXAMPLE 3.8 Crystal Field Stabilization Energies for Metal ions in Octahedral Complexes.
By assigning a value of 0.4
o
for each electron in a t
! 2
orbital, and -0.6
o
for each electron in an e
!
orbital
(see Figure 3.4b), the crystal field stabilization energy of an octahedral complex can be calculated. Determine the
CFSE for the following octahedral complexes:
(a) high spin d
4
(b) low spin d
4
(c) high spin d
7
(d) low spin d
7
Solution
(a) High spin d
4
: In this case the d electrons experience a weak field and therefore are unpaired. Thus the electron
distribution is t
3
! 2
e
1
!
. Therefore if n
t
and n
e
respectively represent the number of electrons in the t ! 2 and e
g
orbitals, then the crystal field stabilizing energy is given by:
CFSE = n
t
(0.4
o
) + n
e
(-0.6
o
)
= (3) (0.4
o
) + (1) (-0.6
o
) = 0.6
o
(b) Low spin d
4
: Now all the electrons are paired and they reside only in the t
! 2
orbitals (see Table 3.4). Thus
CFSE = (4)(0.4

) + 0 = 1.6
o
(c) High spin d
7
: The corresponding electron distribution is t
#
! 2 e
2
! . Thus
CFSE = (5) (0.4
o
) + 2(-0.6
o
) = 0.8
o
(d) Low spin d
7
: the electron distribution is t
0
! 2 e
1
! . Accordingly
CFSE = (6) (0.4
o
) + 1(-0.6
o
) = 1.8
o

EXAMPLE 3.9 Crystal field theory and the structure of complexes
With the acid of crystal field theory rationalize the following observations.
(a) If a divalent ion from the first row of transition metals forms a low-spin complex with a coordination
number of four, the complex is most likely to be square.
(b) Metal ions from the second and third series of transition elements tend to form square complexes more
readily than those of the first.
(c) In the presence of strong ligand fields, square planar complexes are most likely to be formed by d
8
and d
9
metal ions followed by d
7
.
Solution
(a) We are concerned here with a coordination number of four. Thus we need to choose between a square and
a tetrahedral complex. Referring to Table 3.3, it is seen that, for a given d
n
configuration (1< n < 9), the
crystal field stabilization energy (CFSE) value for a low-spin square complex is higher than that for the
corresponding low-spin tetradedral complex. Thus it is reasonable to expect that square complexes would
be preferred.
(b) Since the value of increases from the first to the second and third transition series, one should expect a
corresponding increase in the stability of square complexes.
(c) Ni
2+
is a d
8
ion. It can be seen from Table 3.3 that square d
8
ions exhibit the highest CFSE among the
three possibilities of octahedral, tetrahedral, and square arrangements.

3.4 Hard and Soft Acids and Bases (HSAB)
Metal ions may be divided into two groups, i.e., class (a) or class (b), depending on whether
they prefer to bind to (a) the first elements in groups V, VI, and VII, i.e., N, O, F, or (b) the
second or later members of groups V, VI and VII. That is, complexes of class (a) metals follow
the stability sequence:
F
-
> Cl
-
> Br
-
> I
-
O >> S > Se > Te
N >> P > As > Sb > B
On the other hand class (b) metals tend to follow the reverse order, i.e.,
I
-
> Br
-
> Cl
-
> F
-
Te ~ Se ~ S >> O
P >> N
When an atom is subjected to an electric field there is a tendency for the electronic cloud
surrounding the atom to experience some distortion and an atom is said to be highly polarizable
if its electron cloud is readily distorted. The polarizability of the electron cloud increases, the
further removed it is from the atomic nucleus. Thus, large atoms or molecules which are highly
resistant towards polarization are termed hard while highly polarizable atoms are called soft.
Accordingly, N, O, and F are respectively the hardest (or least polarizable) atoms in groups V,
VI, and VII respectively. It can be stated therefore that class (a) metal ions prefer the hardest
atom of a group, whereas class (b) metal ions prefer the softest atom of a group.
Class (a) metal ions have a low polarizability while class (b) metal ions are highly
polarizable. Thus, class (a) metal ions may be identified as hard Lewis acids while class (b)
metal ions are soft Lewis acids. Therefore, the principle of hard and soft acids and bases (the
HSAB principle) may be stated thus: hard acids prefer hard bases while soft acids prefer soft
bases. Tables 3.6 and 3.7 present a classification of selected ions and molecules according to the
HSAB principle.
The most typical group (a) metal cation has a rare-gas configuration (d
0
cations), e.g. Be
2+
,
Mg
2+
, Ca
2+
, Sr
2+
, Ba
2+
and forms stable aqueous-soluble complexes only with ligands which
have F and O as donor atoms. On the other hand the most typical group (b) cation is
characterized by an outer shell of 18 electrons (d
10
), e.g. Cu
+
, Ag
+
, Zn
2+
, Cd
2+
, Hg
2+
.
Table 3.6 Selected Hard and Soft Bases

Hard Borderline Soft
H
2
O, OH
-
, F
-
C
6
H
5
NH
2
, C
5
H
5
N, R
2
S, RSH, RS
-
CH
3
COO
-
, PO, SO Br
-
, NO
2
-
, SOI
-
, SCN
-
, S
2
O
Cl
-
, CO, ClO, NO R
3
P, R
3
As, (RO)
3
P
ROH, RO
-
, R
2
O CN
-
, RNC, CO
NH
3
, RNH
2
, N
2
H
4
C
2
H
4
, C
6
H
6
, H
-
, R
-

Table 3.7 Selected Hard and Soft Acids

Hard Borderline Soft
H
+
, Li
+
, Na
+,
K
+
Fe
2+
, Co
2+
, Ni
2+
, Cu
2+
, Zn
2+
Cu
+
, Ag
+
, Au
+
, Tl
+
, Hg
+
Be
2+
, Mg
2+
, Ca
2+
,Sr
2+
,Mn
2+
Pb
2+
, Sn
2+
, Sb
3+
, Bi
3+
Pd
2+
, Cd
2+
, Pt
2+
, Hg
2+
Al
3+
, Sc
3+
, Ga
3+
, In
3+
Rh
3+
, Ir
3+
, SO
2
, CH
3
Hg
+
, Co(CN)
La
3+
, Gd
3+
, Lu
3+
Ru
2+
, Os
2+
, GaH
3
Pt
4+
, Te
4+
Cr
3+
, Co
3+
, Fe
3+
, As
3+
, H
3
Sn
3+
Si
4+
, Ti
4+
, Zr
4+
, Th
4+
, U
4+
Pu
4+
, Ce
3+
, Hf
4+
, WO
4+
, Sn
4+
UO, (CH
3
)
2
Sn
2+
, VO
2+
, MoO
3+

A convenient (but admittedly oversimplified) way to rationalize the observed preferential
hard-hard and soft-soft acid-base interaction is to assume that the interactions of hard acids are
primarily via ionic bonding whereas soft acids interact primarily via covalent bonding. It then
follows, from an electrostatic standpoint, that bases which are highly negatively charged and are
small in size will bind most strongly to hard acids. In the case of soft acids, the presence of d
electrons plays a critical role in the bonding interactions. These d electrons may be donated to
appropriate ligands to yield -bonds. Consequently the most likely ligands are those whose
ligand atom (e.g. P, As, S, I) contains empty d orbitals which can accept d electrons from the
metal.
EXAMPLE 3.10 Comparison of stability constants for acid-base reactions.
Consider the following reactions:
H
+
+ CH
3
HgOH = H
2
O + CH
3
Hg
+
(1)
H
+
+ CH
3
HgS
-
= HS
-
+ CH
3
Hg
+
(2)
Speculate on the relative values of the equilibrium constants for Equations 1 and 2 (see Pearson, Science, 151, 172-
177 (1966)).
Solution
According to Tables 3.5 and 3.6, H
+
and CH
3
Hg
+
are hard and soft acids respectively, while OH
-
and S
2-
are
hard and soft bases respectively. In Equation 1 a hard acid (H
+
) reacts with a hard base (OH
-
) to give H
2
O and this
should be a favorable reaction according to the HASB principle. On the other hand, in Equation 2 the hard acid
(H
+
) reacts with the soft base (S
2-
) and this is less favorable. Thus it is expected that the equilibrium constant (K
1
)
for reaction 1 would be greater that the corresponding value (K
2
) for reaction 2. (In fact, it is found that log K
1
=
6.3, and log K
2
= -8.4, in agreement with the predictions of the HASB principle).

EXAMPLE 3.11 Symbiotic behavior and the HSAB principle
It is observed that an acid becomes softer when it is bound to a soft base. This symbiotic effect is attributable to
the ability of the soft base to release electrons to the metal ion, thereby causing a decrease in the effective positive
charge of this ion.
(a) Compare the effective positive charge on the boron atom in BH
3
and in BF
3
.
(b) Discuss the likelihood of forming the complexes BH
3
CO and BF
3
CO.
(c) Speculate on the relative stabilities of the following pairs of complexes: (i) Co(NH
3
)
5
F
2+
, Co(NH
3
)
5
I
2+
; (ii) Co(CN)
5
I
3-
, Co(CN)
5
F
3-
.
Solution
(a) It can be seen from Table 3.5 that the hydride ion (H
-
) is a soft base whereas the fluoride ion (F
-
) is a hard
base. Now, the oxidation state of boron is B
3+
in both BH
3
and BF
3
. Thus in the case of BH
3
, there is
partial transfer of negative charge from the soft base H
-
to the boron and this results in an effective charge
of less than +3 on the boron atom. On the other hand, there is little tendency for the hard base F
-
to lose its
electrons. Therefore it would be expected that in BF
3
the effective charge on the boron atom would not
differ significantly from +3.
(b) According to Table 3.5 CO is a soft base. Furthermore, it was found in part (a) that the effective charge on
the boron atom is lower in BH
3
compared with BF
3
. Thus BH
3
is a softer acid than BF
3
. Therefore the
soft base CO is more likely to bind to BH
3
than to BF
3
.
(c) (i) From Table 4.4, Co
3+
is a hard acid, NH
3
is a hard base, F
-
is a hard base, and I
-
is a soft base. The
complex Co(NH
3
)
5
3+
is a hard acid-hard base complex and therefore should be stable. Since NH
3
is a
hard base, the charge on the cobalt atom is expected to remain close to +3. Thus Co(NH
3
)
5
3+
will be
expected to be a hard acid. Combination of this complex with the hard base F
-
should therefore give a
relatively stable complex. On the other hand, the Co(NH
3
)
5
I
3+
complex involves hard acid-soft base
interaction, which is not expected to be highly favored. Thus the relative stabilities are expected to follow
the order Co(NH
3
)
5
F
2+
> Co(NH
3
)
5
I
2+
(ii) It can be seen from Table 3.5 that Co(CN)is a soft acid. Consequently the complex Co(CN)
5
I
3-
is based on
soft acid-soft base interaction and is favorable, whereas the complex Co(CN)
5
F
3-
is based on soft acid-
hard base interaction, which is unfavorable. Thus the relative stabilities of the complexes are expected to
follow the order Co(CN)
5
I
3-
> Co(CN)
5
F
3-
.
FURTHER READING
1. J. E. Huheey, E.A. Keiter, and R. L. Keiter, Inorganic Chemistry. Principles of Structure and Reactivity, 4th
ed., HarperColins, 1993.
2. A. G. Sharpe, Inorganic Chemistry, 3rd. ed., Longman, London, 1992.
3. G. L. Miessler and D. H. Tarr, Inorganic Chemistry, Prentice-Hall, Englewood Cliffs, NJ, 1991.
4. D. E. Shriver, P. W. Atkins, and C. H. Langford, Inorganic Chemistry, Freeman, New York, 1990.
5. D. W. Smith, Inorganic Substances, Cambridge, New York, 1990.
6. B. Webster, Chemical Bonding Theory, Blackwell, Oxford, 1990.
7. K. M. Mackay and R. A. Mackay, Introduction to Modern Inorganic Chemistry, 4th ed., Prentice Hall,
Englewood Cliffs, NJ, 1989.
8. F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 5th ed., Wiley New York, 1988.
9. T. Moeller, Inorganic Chemistry: A Modern Introduction, Wiley, New York, 1982.
10. K. F. Purcell and J. C. Kotz, An Introduction to Inorganic Chemistry, Sauders, Philadelphia, 1980.
11. G. I. Brown, A New Guide to Modern Valency Theory, Longmans, London, 1967.
12. F. Basolo and R. C. Johnson, Coordination Chemistry, 2nd ed., Science Reviews, 1986.
13. R. G. Pearson, ed., Hard and Soft Acids and Bases, Dowden, Hutchinson and Ross, Stroudsburg, PA, 1973.
14. R. G. Pearson, "Hard and Soft Acids and Bases, HSAB, Part I: Fundamental Principles", J. Chem. Educ., 45,
581-587 (1968); "Part II*: Underlying Theories", J. Chem. Educ., 45, 643-648 (1968).
15. L. E. Orgel, An Introduction to Transition - Metal Chemistry: Ligand-Field Theory, 2nd ed., Wiley, New
York, 1966.