CML 100: Inorganic Chemistry Contents

 Bonding in Transition Metal Complexes

Limitation of Valance Bond Theory, Crystal Field theory, Instructor: Dr. Sayantan Paria
Application of CFT to explain physical properties, Jahn-Teller
Distortion, Magnetism, Color of transition metal complexes. Room No. MS 726
Phone: 011-2659-6499
 Organometallic Chemistry 5:00 PM to 6:30 PM
Introduction to Organometallic Chemistry, 18-electron rule,
Chemistry of Metal Sandwich and Carbonyl Complexes, Important  Total 11 lectures as
Name reactions, Use of organometallic complexes in catalysis.
powerpoint slides.
 Bioinorganic Chemistry
Introduction to Bioinorganic Chemistry, Oxygen carrier proteins  Two surprise quizzes
(such as hemoglobin, hemocyanin, hemerythrin, etc.) cytochromes,
carbonic anhydrase.

 Isomerism in Coordination Compounds Lecture slides will be

Isomerism is different transition metal complexes available as pdf files from
course coordinators website
Text Books
 Importance of understanding bonding of transition metal complexes
Physical properties of metal complexes
Magnetic properties of metal complexes

paramagnetism ferromagnetism

antiferromagnetism

Experimental hydration enthalpies of the di-positive ions Color of transition metal complexes
Structure and reactivity of metalloenzymes
Ti3+ Cr3+ Mn2+ Fe3+ Co3+ Ni2+ Cu2+

Aqueous solution of different divalent/trivalent first-row

transition metal ions
 Bonding in d-block metal complexes
Valence bond Theory
Hybrid orbitals may be formed by mixing the
characters of atomic orbitals that are close in
energy. The character of a hybrid orbital
depends on the atomic orbitals involved and
their percentage contributions.
Linus Pauling
Nobel Prize, 1954, 1962
Crystal Field Theory dx2‒y2, dz2
dxy, dxz, dyz

ΔO
Δt

dx2‒y2, dz2
dxy, dxz, dyz
This is an electrostatic model and simply uses the ligand electrons to create an electric Hans Bethe
field around the metal centre. Ligands are considered as point charges and there are no Nobel Prize, 1967
metal–ligand covalent interactions.
 Bonding in d-block metal complexes
Molecular Orbital Theory
Molecular orbitals are constructed as linear
combinations of atomic orbitals; there is a high
probability of finding electrons in atomic
orbitals that have large coefficients in the linear
combination; each molecular orbital can be
occupied by up to two electrons.

Robert S. Mulliken Friedrich Hund

Nobel Prize, 1966
 Valence bond Theory: hybridization of atomic orbitals
Coordinati Arrangement of donor Orbitals hybridized Hybrid Example
on number atoms orbital
description
2 Linear s, pz sp [Ag(NH3)2]+
3 Trigonal planar s, px, py sp2 [HgI3]-
4 Tetrahedral s, px, py, pz sp3 [FeBr4]2-
4 Square planar s, px, py, dx2−y2 sp2d [Ni(CN)4]2-
5 Trigonal bipyramidal s, px, py, pz, dz2 sp3d [CuCl5]3-
5 Square-based pyramidal s, px, py, pz, dx2−y2 sp3d [Ni(CN)5]3-
6 Octahedral s, px, py, pz, dx2−y2, dz2 sp3d2 [Co(NH3)6]3+
6 Trigonal prismatic s, dxy, dyz, dzx, dx2−y2, dz2 sd5 [Zr(Me)6]3-
7 Pentagonal bipyramidal s, px, py, pz, dxy, dx2−y2, dz2 sp3d3 [V(CN)7]4-
8 Dodecahedral s, px, py, pz, dxy, dyz, dzx, dz2 sp3d4 [Mo(CN)8]4-
8 Square antiprismatic s, px, py, pz, dxy, dyz, dzx, dx2−y2 sp3d4 [TaF8]3-
9 Tricapped trigonal s, px, py, pz, dxy, dyz, dzx, dz2, dx2−y2 sp3d5 [ReH9]2-
prismatic
 Valence bond Theory: Limitations

[CrIII(H2O)6]3+ [FeIII(CN)6]3-

3d 4s 4p 3d 4s 4p

Vacant orbitals available to accept Vacant orbitals available to accept

ligand electrons ligand electrons

3d 4s 4p 3d 4s 4p
d2sp3 d2sp3

 This diagram is appropriate for all octahedral Cr(III) complexes because the three 3d electrons
always singly occupy different orbitals.
 Valence bond Theory: Limitations
[FeIIIF6]3-  Valence bond theory may rationalize
stereochemical and magnetic
properties, but only at a simplistic level.
 It can say nothing about electronic
3d sp3d2
spectroscopic properties or about the
kinetic inertness that is a characteristic
[NiII(H2O)6]3+ of the low-spin d6 configuration.
 The model implies a distinction between
high- and low-spin complexes that is
actually misleading.
3d sp3d2  Finally, it cannot tell us why certain
ligands are associated with the

4s, 4p and two 4d orbitals participates to form sp3d2 formation of high- (or low-) spin
hybrid orbitals. However, this scheme is unrealistic complexes. These limitations of VB
because the 4d orbitals are at a significantly higher theory necessitate that we must
energy than the 3d atomic orbitals. approach the bonding in d-block metal
complexes in other ways.
The conventional representation of a set of five degenerate d-orbitals

The formation of a
dz2 orbital from a
linear combination
of dz2—y2 and dz2—x2
orbitals.

dz2 dx2—y2

dzx dyz dxy

 Crystal Field Theory: The Octahedral Crystal Filed
Electrons in dz2 and
dx2‒y2 orbitals are
concentrated close to
the ligands, along the
axes, resulting strong
repulsions

d z2 d x2—y2

Hans Bethe
Nobel Prize, 1967

Electrons in dxy, dyz, and dzx

orbitals are concentrated in
regions that lie between the
ligands, resulting in weak
repulsions
d xy d yz d zx
 Crystal Field Theory: The Octahedral Crystal Filed
This is an electrostatic model and simply uses the ligand electrons to create an electric field around the
metal centre. Ligands are considered as point charges and there are no metal–ligand covalent interactions.
The theory concentrates on the resulting splitting of the d orbitals into groups with different energies, and
uses that splitting to rationalize and correlate the optical spectra, thermodynamic stability, and magnetic
properties of complexes. 3d 3d
z2 x2—y2

Orbital
energy
Degenerate
3d atomic orbitals 3dxy 3dyz 3dzx
Degenerate
3d atomic orbitals The 3d atomic orbitals are split
Into two levels

Metal ion Mn+ and six If the electrostatic field created
ligands L at infinite by point charge ligand is
distance away spherical, the energies of the
electrons in the 3d orbitals are
raised uniformly
If the electrostatic filed created by
the point charge ligands in
octahedral, 3d orbitals that points
directly at the ligands have higher
energy
The orientation of the five d orbitals with respect to The energies of the d
the ligands of an octahedral complex: the degenerate orbitals in an octahedral
eg and t2g orbitals crystal field
 A triply degenerate level is labelled t
 A doubly degenerate level is labelled e
 The subscript g means gerade and the
subscript u means ungerade.
 The u and g labels are applicable only
if the system possesses a centre of
symmetry (centre of inversion) and
thus are used for the octahedral field

The magnitude of ΔO is determined by the strength of the crystal field, the two extremes being called
weak field and strong field
ΔO (weak field) < ΔO (strong field)
 ΔO is an experimental quantity and can be evaluated
from electronic absorption spectroscopic data

eg Light of eg

t2g ≈500 nm t2g

t2g1 eg0 t2g0 eg1

Corresponding to an energy change of 243 kJ mol—1

corresponds to ΔO ( 1 cm—1 = 11.96
10—3 kJ/mole)

The optical absorption spectrum of [Ti(OH2)6]3+.

The compound absorbs strongly at around 500

nm (green light), and appears purple
 High-spin vs. Low-spin Complex
 An octahedral 3d4
complex is likely to be
low-spin if the ligand field
is strong but high-spin if
the field is weak; the
same applies to 3d5, 3d6,
and 3d7 complexes.

 For 3d-metal ions, low-

spin complexes commonly
occur for ligands that are
high in the
spectrochemical series
(such as CN—) and high-
The effect of weak and strong ligand fields on the occupation of spin complexes are
4 6
electrons for a d (left )and d (right) complexes. The former results in common for ligands that
a high-spin configuration and the latter in a low-spin configuration. are low in the series (such
ΔO < Pairing energy (P): High-spin complex as F—)
ΔO > Pairing energy (P): Low-spin complex
 Crystal field stabilization energy

d2 d3 d4 d4

high-spin low-spin
CFSE = 2
(‒0.4 ΔO) CFSE = 3
(‒0.4 ΔO) CFSE = 3
(‒0.4 ΔO) CFSE = 4
(‒0.4 ΔO) + P
= ‒0.8 ΔO = ‒1.2 ΔO + 1
(0.6 ΔO) = ‒0.6 ΔO = ‒1.6 ΔO + P
 In an octahedral complex, the first three d electrons of a 3dn complex occupy separate t2g nonbonding
orbitals, and do so with parallel spins. For example, the ions Ti2+ and V2+ have electron configurations 3d2
and 3d3, respectively. The d electrons occupy the lower t2g orbitals as shown above. The energy of a t2g
orbital relative to the barycentre of an octahedral ion is ‒0.4∆O and the complexes are stabilized by 2

(‒0.4∆O) = ‒0.8∆O (for Ti2+) and 3
(‒0.4∆O) = ‒1.2∆O (for V2+). This additional stability, relative to the
barycentre is called the crystal-field stabilization energy (CFSE).

 For a low-spin d4 configuration, the CFSE consists of two terms: the four electrons in the t2g orbitals give
rise to a ‒1.6ΔO term, and a pairing energy, P, accounts for a a strong Coulombic repulsion of two
electrons.
 High-spin = weak field  The strength of the crystal field (as
Low-spin = strong field
dn Electronic CFSE Electronic CFSE measured by the value of ∆O) and
configuration configuration the spin-pairing energy (as
measured by P) depend on the
d1 t2g1eg0 −0.4ΔO identity of both the metal and the
d2 t2g2eg0 −0.8ΔO ligand, so it is not possible to specify
d3 t2g3eg0 −1.2ΔO a universal point in the
spectrochemical series at which a
d4 t2g3eg1 −0.6ΔO t2g4eg0 −1.6ΔO + P
complex changes from high spin to
d5 t2g3eg2 0 5
t2g eg 0 −2.0ΔO + 2P low spin. For 3d-metal ions, low-spin
d6 t2g4eg2 −0.4ΔO t2g6eg0 −2.4ΔO + 2P complexes commonly occur for
ligands that are high in the
d7 t2g5eg2 −0.8ΔO t2g6eg1 −1.8ΔO + P
spectrochemical series (such as CN—
d8 t2g6eg2 −1.2ΔO ) and high-spin complexes are
d9 t2g6eg3 −0.6ΔO common for ligands that are low in
the series (such as F—).
d10 t2g6eg4 0
 The values of ∆O for complexes of 4d- and 5d-series metals are typically higher than for the 3d-series metals.
Pairing energies for the 4d- and 5d-series metals tend to be lower than for the 3d-series metals because the
orbitals are less compact and electron-electron repulsions correspondingly weaker. Consequently, complexes
of these metals generally have electron configurations that are characteristic of strong crystal fields and
typically have low spin.
 Tetrahedral crystal field
 In a tetrahedral complex, none of the metal d orbitals
points exactly at the ligands, but the dxy, dyz and dxz
orbitals come nearer to doing so than the dz2 and dx2—
y2 orbitals.
 The splitting of the d orbitals is therefore inverted
compared with that for a regular octahedral
structure, and the energy difference (Δt) is smaller.


Δt = ΔO ≈ ΔO
 
The crystal field splitting in a tetrahedral field is intrinsically smaller than that in octahedral field
because there are only two-thirds as many ligands and they have less direct effect on the d orbitals.

A rare example
of a low-spin
tetrahedral
complex

Tetrahedral complexes are almost invariably high-spin

n
 Square planar crystal field
 A square-planar arrangement gives the d-orbital
splitting shown here, with dx2‒y2 raised above all the
others. This arrangement may become energetically
Square planar favorable when there is d8 configuration and the
Octahedral Removal of axial complex crystal field is strong enough to favor the low-spin
complex dx2‒y2
ligands d2yzd2zxd2z2d2xy configuration.
dx2‒y2
 Simple theory predicts that ΔSP = 1.3ΔO for
eg
Δ complexes of the same metal and ligands with the
dz2 same M‒L bond lengths.

dxy Examples:
dxy [Ni(CN)4]2-, [PdCl4]2-, [Pt(NH3)4]2+, [PtCl4]2-,
t2g [AuCl4]2-
dz2
dxz, dyz Second and third row metal d8 complexes (e.g. Pt(II),
Pd(II), Rh(I), Ir(I)) are invariably square planar.
dxz, dyz
 Crystal field splitting of some other geometries

L
L L Anionic part of
L [Cr(NH3)6]3+[CuCl5]3‒
L L L L
M L M M L Cl
L L L L
L L
L Cu
Structure of
dz2 dx2‒y2 dz2 [Mn(EDTA)(H2O]‒

dz2 dxy dx2‒y2

Anionic part of
[Cr(en)3]3+[Ni(CN)5]3‒
dxy dx2‒y2 dxy N O
N Mn
dxz dyz dxz dyz dxz dyz
Ni
Trigonal bipyramidal Square pyramidal Pentagonal bipyramidal OH2
(TBP) (SP)