COORDINATION CHEMISTRY

Introduction
• Coordination Chemistry is the study of
compounds that have a central atom (often
metallic) surrounded by molecules or anions,
known as ligands.
• The ligands are attached to the central atom
by dative bonds, also known as coordinate
bonds, in which both electrons in the bond
are supplied by the same atom on the ligand.
• Coordination compounds are complexes that
consist of one or more central atoms or ions
with one or more attached molecules.
Introduction
• The central atom is called a metal, and is a
Lewis Acid; The attached ions are ligands,
and are Lewis Bases; The total number of
attachments between metal and ligands is
the coordination number.
 Overview of Crystal Field Theory
• According to crystal field theory, the interaction
between a transition metal and ligands arises from
the attraction between the positively charged metal
cation and the negative charge on the non-bonding
electrons of the ligand.
• The theory is developed by considering energy
changes of the five degenerate d-orbitals upon being
surrounded by an array of point charges consisting of
the ligands.
 Overview of Crystal Field Theory
• As a ligand approaches the metal ion, the
electrons from the ligand will be closer to
some of the d-orbitals and farther away from
others, causing a loss of degeneracy.
• The electrons in the d-orbitals and those in
the ligand repel each other due to repulsion
between like charges. Thus the d-electrons
closer to the ligands will have a higher energy
 Crystal Field Splitting:
• Splitting of degenerate d orbital into different
energy levels is called ( mostly t2g and eg)
crystal field splitting.
• Crystal Field Splitting Energy (Δ):
• The energy difference between t2g and eg
orbitals is called Crystal Field Splitting Energy
(Δ)
 Crystal Field Splitting in Octahedral Complexes
• The most common type of complex is octahedral, in
which six ligands form the vertices of an octahedron
around the metal ion.
• In octahedral symmetry the d-orbitals split into two sets
with an energy difference, Δoct (the crystal-field splitting
energy, also commonly denoted by Δoct or 10Dq) where
the dxy, dxz and dyz orbitals will be lower in energy than
the dz2 and dx2-y2, which will have higher energy, because
the former group is farther from the ligands than the
latter and therefore experiences less repulsion.
• The three lower-energy orbitals are collectively referred
to as t2g, and the two higher-energy orbitals as eg.
 Crystal Field Splitting in Tetrahedral Complexes
• Tetrahedral complexes are the second most common type;
here four ligands form a tetrahedron around the metal ion.
• In a tetrahedral crystal field splitting, the d-orbitals again split
into two groups, with an energy difference of Δtet. The lower
energy orbitals will be dz2 and dx2-y2, and the higher energy
orbitals will be dxy, dxz and dyz - opposite to the octahedral
case.
• Furthermore, since the ligand electrons in tetrahedral
symmetry are not oriented directly towards the d-orbitals, the
energy splitting will be lower than in the octahedral case.
• The crystal field splitting energy for tetrahedral metal
complexes (four ligands) is referred to as Δtet, and is roughly
equal to 4/9Δoct (for the same metal and same ligands).
Crystal Field Splitting in Tetrahedral Complexes
Crystal field splitting in Tetrahedral
Complexes
 Crystal field stabilization energy
• The use of these splitting diagrams can aid in the
prediction of magnetic properties of coordination
compounds. A compound that has unpaired
electrons in its splitting diagram will be
paramagnetic and will be attracted by magnetic
fields, while a compound that lacks unpaired
electrons in its splitting diagram will be
diamagnetic and will be weakly repelled by a
magnetic field.
 Crystal Field Stabilization Energy
• The crystal field stabilization energy (CFSE) is the stability that
results from placing a transition metal ion in the crystal field
generated by a set of ligands.
• It arises due to the fact that when the d-orbitals are split in a
ligand field (as described above), some of them become lower in
energy than before with respect to a spherical field known as
the barycenter in which all five d-orbitals are degenerate.
• For example, in an octahedral case, the t2g set becomes lower in
energy than the orbitals in the barycenter. As a result of this, if
there are any electrons occupying these orbitals, the metal ion is
more stable in the ligand field relative to the barycenter by an
amount known as the CFSE.
 Crystal Field Stabilization Energy
• Conversely, the eg orbitals (in the octahedral case) are
higher in energy than in the barycenter, so putting
electrons in these reduces the amount of CFSE.
• If the splitting of the d-orbitals in an octahedral field is Δoct,
the three t2g orbitals are stabilized relative to the
barycenter by 2/5 Δoct, and the eg orbitals are destabilized by
3
/5 Δoct.
• CFSE values are calculated using the formula
CFSE = -0.4 (t2g)m Δo + 0.6 (eg)n Δo + x P
Where m = no of electrons in t2g orbitals, n = no of
electrons in eg orbitals, P = mean pairing energy and x = no.
of paired electons.
 CFSE Values of Octahedral Complexes

Electron High-spin Low-spin

Configurati
on
d1 t2g1 eg0 -0.4 Δo t2g1 eg0 -0.4 Δo

d2 t2g2 eg0 - 0.8 Δo t2g2 eg0 - 0.8 Δo

d3 t2g3 eg0 -1.2 Δo t2g3 eg0 -1.2 Δo
d4 t2g3 eg1 - 0.6 Δo t2g4 eg0 -1.6 Δo + P
d5 t2g3 eg2 0.0 Δo t2g5 eg0 -2.0 Δo + 2P

d6 t2g4 eg2 -0.4 Δo t2g6 eg0 -2.4 Δo + 2P

 CFSE Values of Tetrahedral Complexes
• Tetrahedral splitting is seldom large enough to result in pairing of the
electrons. As a result, low-spin tetrahedral complexes are not
common. A rare example is Cr[N(SiMe3)2]3[NO].
Electron Configuration High-spin
d1 e1 t20 - 0.6 Δt

d2 e2 t20 - 1.2 Δt
d3 e2 t21 - 0.8 Δt
d4 e2 t22 - 0.4 Δt
d5 e2 t23 - 0.0 Δt
d6 e3 t23 - 0.6 Δt
d7 e4 t23 - 1.2 Δt
d8 e4 t24 - 0.8 Δt

d9 e4 t 5
- 0.4 Δt
 Magnetic Properties of Metal Complexes
• An interesting characteristic of transition metals is their ability to
form magnets. Metal complexes that have unpaired electrons
are magnetic. Since the last electrons reside in the d orbitals, this
magnetism must be due to having unpaired d electrons.
• The spin of a single electron is denoted by the quantum number
ms as +(1/2) or –(1/2). This spin is negated when the electron is
paired with another, but creates a weak magnetic field when the
electron is unpaired.
• More unpaired electrons increase the paramagnetic effects. The
electron configuration of a transition metal (d-block) changes in
a coordination compound; this is due to the repulsive forces
between electrons in the ligands and electrons in the compound.
• Depending on the strength of the ligand, the compound may be
paramagnetic or diamagnetic.
 Magnetic Properties of Metal Complexes
• When an electron in an atom or ion is unpaired, the magnetic
moment due to its spin makes the entire atom or ion paramagnetic.
• The size of the magnetic moment of a system containing unpaired
electrons is related directly to the number of such electrons: the
greater the number of unpaired electrons, the larger the magnetic
moment.
• Therefore, the observed magnetic moment is used to determine
the number of unpaired electrons present.
• The measured magnetic moment of low-spin d6 [Fe(CN)6]4−
confirms that iron is diamagnetic, whereas high-spin d6 [Fe(H2O)6]2+
has four unpaired electrons with a magnetic moment that confirms
this arrangement.
• Paramagnetism (spin only) is calculated using the equation Square
root of n (n+2)
 The following table gives an idea about the paramagnetic behavior
of metal complexes in octahedral fields of strong and weak
Electron Strong Field Complexes Weak Field Complexes
configurati
on
Distributio No. of µeff Distributio No. of µeff
n unpaired B.M.
n unpaired B.M.
of electrons of electrons
electrons electrons
d1 t2g1 eg0 1 1.72 t2g1 eg0 1 1.72
d2 t2g2 eg0 2 2.83 t2g2 eg0 2 2.83
d3 t2g3 eg0 3 3.87 t2g3 eg0 3 3.87
d4 t2g4 eg0 2 2.83 t2g3 eg1 4 4.89
d5 t2g5 eg0 1 1.72 t2g3 eg2 5 5.91
d6 t2g6 eg0 0 0 t2g4 eg2 4 4.89
d7 t2g6 eg1 1 1.72 t2g5 eg2 3 3.87
d8 t2g6 eg2 2 2.83 t2g6 eg2 2 2.83
d9 t2g6 eg3 1 1.72 t2g6 eg3 1 1.72
Magnetictic Properties of Tetrahedral
Complexes

Electron Configuration Distribution Unpaired Electrons µeff (B.M.)

d1 e 1 t2 0 1
1.72
2 2.83
d2 e 2 t2 0
3 3.87
d3 e 2 t2 1
4 4.89
d4 e 2 t2 2
5 5.91
d5 e 2 t2 3
4 4.89
d6 e 3 t2 3
3 3.87
d7 e 4 t2 3
2 2.83
d8 e 4 t2 4
1 1.72
d9 e 4 t2 5
0
d10 e 4 t2 6
 Molecular Orbital Theory
• Crystal field theory fails to explain many physical properties of
the transition metal complexes because it does not consider the
interaction of metal and ligand orbitals.
• The molecular orbital theory can be very well applied to
transition metal complexes to rationalize the covalent as well
as ionic character of M-L bond.
The important LCAO rules are
• The atomic orbital of the metal and the ligands combine to
form new orbitals, known as molecular orbitals.
• The number of molecular orbital formed will be equal to the
number of atomic orbitals combined.
• The molecular orbitals formed are two types. Bonding
molecular orbitals and anti bonding molecular orbitals.
• The energy of bonding molecular orbitals is less than that of
energy of atomic orbitals. However, the energy of anti-bonding
orbitals is more than that of energy of atomic orbitals
• The energy of non bonding orbitals remain same.
 MOED of Octahedral Complexes
• σ bonding only (No Metal- Ligand π-bonding)
• Let’s take [Co(NH3)6]3+ as an example. Using the LGO method,
one can construct a qualitative MO diagram for bonding in a
[ML6]n+ complex.
• For the first row transition metals, what are the valence atomic
orbitals?
• Six LGO (Ligand group orbitals) that have symmetries that
match the s, p and dz2 and dx2-y2 orbitals.
• How many MO will result from the overlap of the LGO’s with
the metal orbitals? Will any of the metals d-orbitals remain
non-bonding? If yes, which ones?
 MOED of Octahedral Complexes
• σ bonding only (No Metal- Ligand π-bonding)
• Let’s take [Co(NH3)6]3+ as an example. Using the LGO method, one can
construct a qualitative MO diagram for bonding in a [ML6]n+ complex.
• For the first row transition metals, what are the valence atomic orbitals?
• Six LGO (Ligand group orbitals) that have symmetries that match the s, p and
dz2 and dx2-y2 orbitals.
• How many MO will result from the overlap of the LGO’s with the metal
orbitals? Will any of the metals d-orbitals remain non-bonding? If yes, which
ones?
• Label the MO diagram with the appropriate atomic orbitals on the metal, and
the symmetry labels of the resulting MO’s.
[Remember those orbitals which are symmetric with respect to an inversion
center are labeled g, and those that are asymmetric with respect to i are
labeled u.]
 Structures of the Molecules:
Molecules are held together by shared electron pairs, or
covalent bonds. Such bonds are directional, meaning that the
atoms adopt specific positions relative to one another so as
to maximize the bond strengths. As a result, each molecule
has a definite, fairly rigid structure, or spatial distribution of
its atoms.
 VSEPR Model
•The VSEPR model can predict the structure of nearly any molecule
or polyatomic ion in which the central atom is a nonmetal, as well
as the structures of many molecules and polyatomic ions with a
central metal atom.
•The premise of the VSEPR theory is that electron pairs located in
bonds and lone pairs repel each other and will therefore adopt the
geometry that places electron pairs as far apart from each other as
possible.
•This theory is very simplistic and does not account for the
subtleties of orbital interactions that influence molecular shapes;
however, the simple VSEPR counting procedure accurately predicts
the three-dimensional structures of a large number of compounds,
which cannot be predicted using the Lewis electron-pair approach.
 VSEPR Model
• We can use the VSEPR model to predict the geometry of most
polyatomic molecules and ions by focusing only on the number
of electron pairs around the central atom, ignoring all other
valence electrons present.
• According to this model, valence electrons in the Lewis structure
form groups, which may consist of a single bond, a double bond,
a triple bond, a lone pair of electrons, or even a single unpaired
electron, which in the VSEPR model is counted as a lone pair.
Because electrons repel each other electrostatically, the most
stable arrangement of electron groups (i.e., the one with the
lowest energy) is the one that minimizes repulsions.
• Groups are positioned around the central atom in a way that
produces the molecular structure with the lowest energy
The following examples will illustrate the shapes
of the few molecules.
 This VESPR procedure is summarized as follows:
• Draw the Lewis electron structure of the molecule or
polyatomic ion.
• Determine the electron group arrangement around the
central atom that minimizes repulsions.
• Assign an AXmEn designation; then identify the LP–LP, LP–BP,
or BP–BP interactions and predict deviations from ideal
bond angles.
• Describe the molecular geometry.