Welcome to CHEM-502

Chemistry of Coordination Compounds

 My Profile
• Dr. Abdulmalik
• Associate Professor, Chemistry Department, KFUPM,
Room #4-229, Tel: 7552; Email: [email protected]
• Post-Doctoral Fellow at King Abdullah University of
Science and Technology (KAUST)

• Post-Doctoral Fellow at Texas A&M University at Qatar

• Obtained my Ph.D. from National University of Singapore

(NUS) in 2010
H. Deng, et. al Science, 336, 1018-1023 (2012)
 Syllabus

Course Credit: 3-0-3 Prerequisites: Two semesters of

undergraduate inorganic chemistry

• Textbook: J. R. Gispert, "Coordination Chemistry".

• References:
– 1. Inorganic Chemistry by Huheey
– 2. Inorganic Chemistry by G. L. Miessler and D. A. Tarr
– 3. Inorganic chemistry, D. F. Shriver, P. W. Atkins and C. H. Langford
– 4. Physical Inorganic Chemistry , A coordination chemistry Approach.
S.F.A Kettle
– 5. Ligand Field theory and its applications, B. R. Figgis and M. A.
Hitchman
 Course Learning Outcomes

1 Knowledge and Understanding

1.1 Classify correctly the types of ligands, stereochemistry and isomerism in
coordination compounds.
1.2 Describe correctly important examples of supra-molecular chemistry,
host-guest and self-assembly processes and the chemistry of
coordination polymers and metal-organic frameworks.
2 Skills
2.1 Apply correctly theories of bonding to coordination compounds.

2.2 Discuss competently the mechanisms of important reactions in

coordination chemistry.
2.3 Present competently an oral report on a piece of research work in
coordination chemistry.
Topics:
1. Bonding in Coordination Compounds
2. Classification of Ligands and Design of Coordination
3. Stereochemistry and Distortions in Coordination Compounds
4. Isomerism in Coordination Compounds
5. Reactions of Coordination Compounds and Mechanisms
6. Metal-Metal Bonds and Metal Clusters
7. Supramolecular Chemistry
8. Crystal Engineering and Metal-Organic Frameworks
 Grading Policy
Distribution of Points
First Major Exam 25 %
Second Major Exam 25 %
Final Exam 30 %
Home Work / Assignments 10 %
Term paper and Presentation 10 %
----------------------------------------------------
Total 100 %
Attendance: If the unexcused absences exceed 6, the student will be given
a DN grade
Exam and homework schedule:
Students are responsible to monitor all official announcements in Blackboard:
- First major exam: Saturday, March 01, 7:30 PM
- Second major exam: Saturday, April 26, 8:00 PM
- Final exam: To be announced later
 Review the following
I. Chapter 2 (from Inorganic Chemistry by G. L. Miessler and D. A. Tarr)
II. Chapter 4 (Inorganic Chemistry by G. L. Miessler and D. A. Tarr)
III. Chapter 9(Inorganic Chemistry by G. L. Miessler and D. A. Tarr)
 Coordination Compounds

I. Coordination compounds
– compounds composed
of a metal atom or ion
and one or more ligands.
A. Examples
B. Ligands usually donate
electrons to the metal
C. Includes organometallic
compounds
 Alfred Werner
I. Alfred Werner (12 December 1866 – 15 November 1919) was a Swiss
chemist who was a student at ETH Zurich and a professor at the University
of Zurich. He won the Nobel Prize in Chemistry in 1913 for proposing the
octahedral configuration of transition metal complexes.
 Werner’s Coordination Chemistry

I. Performed systematic studies to understand bonding

in coordination compounds.
A. Organic bonding theory and simple ideas of ionic charges
were not sufficient.
II. Two types of bonding
A. Primary – molecules or ion (ligands) are attached directly
to the metal ion.
B. Secondary – positive charge of the metal ion is balanced
by negative ions in the compound.
1) Coordination sphere or complex ion.
Werner’s Theory
a) Metals interact with 6 ligands in octahedral geometry to form “complex ions”
i. Primary or Inner Coordination Sphere = ligands with bonds to Metal
ii. Secondary or Outer Coordination Sphere = more loosely bound
anions present only to balance charge

b) Explains multiple complexes of the same sets of ligands in diff. numbers

i. [Co(NH3)6]Cl3 [Co(NH3)5Cl]Cl2 [Co(NH3)4Cl2]Cl [Co(NH3)3Cl3]
ii. Different numbers of ions are produced due to outer sphere dissociation

c) Explains multiple complexes with exact same formula = isomers

 Werner’s Coordination Chemistry

I. He largely studied compounds with four or six

ligands.
A. Octahedral and square-planar complexes.
II. It was illustrated that a theory needed to account for
bonds between ligands and the metal.
A. The number of bonds was commonly more than accepted at
that time.
III. New theories arose to describe bonding.
A. Valence bond, crystal field, and ligand field.
 Chelating Ligands

I. Chelating ligands trisoxalatochromate(III) ion or just [Cr(ox)3]3-

(chelates) – ligands that
have two or more points
of attachment to the
metal atom or ion.
A. Bidentate, tridentate,
tetra.., penta…, hexa…
(EDTA).
 Bonding in Coordination compounds

Objectives:

1. Crystal field Theory

2. Molecular Orbital and Ligand Field Theories

3. Angular Overlap Model

Atomic Orbitals
 The Schrödinger Equation
• Describes wave properties of electrons: position, mass, total E, potential E
• Y = wave function = describes an electron wave in space = describes atomic
orbital
• The Schrödinger Equation:

H = the Hamiltonian Operator = calculus operation on Y

HΨ = EΨ E = energy of the electron
– When H is carried out on Y , the result is E times Y (E is a constant)
b) Different orbitals have different Y and consequently, different E’s

• The Hamiltonian Operator for one electron system

− h2   2  2  2  Ze 2
H = 2  2 + 2 + 2  −
8 m  x y z  4 o x 2 + y 2 + z 2

Kinetic Energy part Potential Energy part

 – Definitions
» h = Planck’s constant
» m = mass of the particle
» E = total energy of the system
» e = charge of electron
» (x2 + y2 + z2)1/2 = r = distance to nucleus
» Z = charge of the nucleus
» 4o = permittivity of vacuum

– Applied to Y:

 − h2   2  2  2  
 2  2 + 2 + 2  + V ( x, y, z ) Y ( x, y, z ) = EY ( x, y, z )
 8 m  x y z  
– V = potential E = electrostatic attraction between electron/nucleus
− Ze 2 − Ze 2
V= =
4 o x +y +z
2 2 2 4 o r
» Define attractive force = negative energy
» Closer to nucleus = large –V; farther from nucleus = small –V
» if r goes to ∞, then V = 0
5) There is an number of solutions to the Schrödinger equation, each describing an
electron in an atomic orbital: 1s, 2s, 2px, 2py….
6) The meaning of Y
– Y has no physical meaning itself, it is just a mathematical expression
– Y2 = probability of finding the electron at a given point in space
» If you consider all space, Y2 = 100%
» Consider where the electron is 90% of the time, Y2 = atomic orbital (1s)
7) Physical Reality imposes some conditions on what Y can be
– Y must have only one value because a given electron only has one energy
b) Y and dY must be continuous because the electron can’t “jump”
c) Y ----> 0 as r ----> ∞ because the probability must decrease farther away
d) The total probability of finding the electron somewhere must = 1
» Normalization = setting values to 1

Y Y d = 1
*
A A

8) All orbitals are orthogonal :

Y* is used to make imaginary Y real

just use Y2 if not imaginary
 Applications of Quantum Mechanics
B. Atomic Wave Functions
• Solving a 3D problem: positively charged nucleus and one negative electron
– Use methods similar to Particle in a Box to find E and Y
– For a 1D problem, we generated one quantum number = n
– For a 3D problem, we will generate 3 quantum numbers= n, l, ml
– Later, we will add the 4th quantum number to describe e spin (ms)

• Quantum Numbers
– n = principle quantum number = responsible for Energy of electron
– l = orbital angular momentum = responsible for shape of orbital
– ml = magnetic angular momentum = responsible for orbital position in space
– ms = spin angular momentum = describes orientation of e- magnetic moment
– When no magnetic field is present, all ml values have the same energy and
both ms values have the same energy
– Together, n, l, and ml define one atomic orbital
Quantum Numbers
3) Spherical Coordinates
– Cartesian Coordinates: x, y, z define a point Conversions:
– Spherical Coordinates: r, q, f define a point x = r sinq cosf
» r = distance from nucleus to the electron y = r sinq sinf
» q = angle from the z-axis (from 0 to ) z = r cosq
» f = angle from the x-axis (from 0 to 2)

Spherical Volumes:
3 sides = rdq, r sinq df, and dr
dV = product = r2 sinq dq df dr
c) In Spherical Coordinates, Y is the product of the angular factors

» Radial factor describes e- density at different distances from nucleus

» Angular factor describes shape of orbital and orientation in space

» Y(r,q,f) = R(r)Q(q)F(f) = R(r)Y(q,f)

[Y combines angular factors]
4) The Radial Function

– R(r) is determined by n, l
– Bohr Radius = ao =52.9 pm = r at Y2 maximum probability for a H 1s
orbital
» Used as a unit of distance for r in quantum mechanics (r = 2ao,
etc…)
– Radial Probability Function = 4r2R2
» Describes the probability of finding e- at a given distance over all
angles
» Plots of R(r) and 4r2R2 use r scale with ao units
» Electron Density falls off rapidly as r increases
» For 1s, probability = 0 by the time r = 5ao
» For 3d, max prob is at r = 9ao ; prob = 0 at r = 20ao
» All orbitals have prob = 0 at the nucleus 4r2R2 = 0 at r = 0
» Maxima: combination of rapid increase of 4r2 with r and the
rapid decrease of R2 with r
» Shape and distance of e- from nucleus determine reactivity
Radial Functions
Radial Probability Functions
5) The Angular Functions
– q(q) and F(f) show how the probability changes at the same distance, but
different angles = shape/orientation of the atomic orbitals

– Angular factors are determined by l and ml : Ylm

» Y2 = probability is same for +/-
6) Nodal Surfaces = surfaces where Y2 = 0 (Y changes sign)
– Appear naturally from Y mathematical forms
– 2s orbital: Y changes sign at r = 2ao giving a nodal sphere
– Y2 = prob = 0 for finding the electron here
– Y(r,q,f) = R(r)Y(q,f) and Y2 = 0
» Either R(r) = 0 or Y(q,f) = 0
» Determines Nodal Surfaces by finding these conditions

– Radial Nodes = Spherical Nodes R(r) = 0

» Gives Layered appearance of orbitals
» R(r) changes sign
» 1s, 2p, 3d have no radial nodes
» Number of radial nodes increases with n
» Number of radial nodes = n – l -1
Radial Probability Functions
Examples of Angular and Radial
Nodes
Radial (spherical) nodes
Angular Nodes: Y = 0 = planar or conical
a) Easiest to see in Cartesian Coordinates (x, y, z)
b) Can find where Y changes from +/-

Example 1
a) pz
b) pz because z appears in the Y expression
1 3z
c) Y = 0 for angular node: z = 0 = xy plane is a node Y=  
d) Y = + where z > 0, Y is – where < 0 2  r
e) 2pz has no spherical nodes
 Angular Nodes in 3dx2-y2

j) Example 2 Y=
(
1 15 x 2 − y 2 )
a) 3dx2-y2 4  r2
b) Y = 0 when x = y and x = -y
c) Nodal planes contain z-axis and make 45o angle with x and y axes
d) Y = + when x2 > y2 and Y = - when x2 < y2
e) No spherical nodes
Determine Total, angular, radial nodes

Total nodes: n-1

4s 7f 6d 3p
Angular 0 3 2 1
Radial 3 3 3 1
Total nodes 3 6 5 2
Bonding in Coordination compounds

Objectives:
1. Crystal field Theory
2. Molecular Orbital Theory / Ligand field theory
3. Angular Overlap Model
Examples of Coordination compounds
a) Simple Covalent Bond = bond formed by the sharing of one
electron from each member. H3C• + •H H3C—H

b) Coordination Bond = bond formed by the donation of both

electrons from one member. H3N: + Ni2+ Ni2+—NH3

c) Other non-covalent interactions N

H
i. Hydrogen Bonding N N
H
N
H H

ii. − Interactions N

Application of Crystal Field Theory
Case of an octahedral Field
Splitting of d orbitals in an octahedral
field
Quantitative Aspects
 Ligand Field Stabilization Energy = LFSE
• LFSE = energetic stabilization of the d-electrons due to orbital
splitting (measured in units of Do)
• Treat electrons in t2g orbitals as stabilized by –2/5 Do and
electrons in eg* orbitals as destabilized by +3/5 Do

LFSE =

LFSE =
Only d4 – d7
metals
have
differences
between
high and
low
spin
 Dq=Differential of quanta

Δo > P = Tend to form low spin (strong field)

Δo < P = Tend to form high spin (weak field)

ΔO=10 Dq
 Spectrochemical Series
I− < Br− < S2− < SCN-< Cl− < NO3− < N3−, F− < OH− < <
C2O42- < O2- < H2O < NCS- < CH3CN < NH3 ~ py <
en < bipy < phen < NO2− < PPh3 < CN− < CO

- Halides : F->Cl->Br->I- (due to smallest anion has more repulsion energy with decreasing r)
- 10Dq increases with oxidation number
- 10 Dq increases upon moving down a group: First to second: 50%, second to third: 25%
- Δo increases with increasing principal quantum number: Δo (3d) < Δo (4d) < Δo (5d)
Δo > P = Tend to form low spin (strong field)
Δo < P = Tend to form high spin (weak field)
Square planar Complexes
D4h symmetry
Square planar Complexes
D4h symmetry
 d Orbital Splitting
In Tetrahedral Complexes
Tetrahedral Field