CHM102A: General Chemistry

Inorganic Chemistry: Crystal Field Theory and Structure of

Coordination Complexes, Oxidative Addition, Reductive
Elimination, Insertion Reactions, Hydrogenation,
Hydroformylation, Monsanto Acetic Acid Process and Ziegler-
Natta Polymerization.

Sabuj Kundu
sabuj@iitk.ac.in
 Coordination Complex
❑ A coordination complex: in which ligands (neutral molecules or
anions) bond to a central metal atom (or ion) by coordinate
covalent bonds.

❑ Within a ligand, the atom that is directly bonded to the metal

atom/ion is called the donor atom.
 Coordination Complex
❑ Coordinate covalent bond: in which the donor atom supplies both electrons.
This type of bonding is different from a normal covalent bond in which each
atom supplies one electron.
❑ Properties of coordination compounds are different from the metal atom/ion
and ligands from which they are composed.
❑ Complex ion: If coordination complex carries a net charge.
❑ Coordination sphere: consists of the central metal atom plus its attached ligands.
❑ The coordination number is the number of donor atoms bonded to the central
metal atom.
 Coordination Complex: Ligands
Ligands: the molecules or ions that surround the metal in a complex;
must contain at least one unshared pair of valence electrons

❑ Coordination number: number of donor atoms surrounding the

central atom

❑ Classifications of ligands: Monodentate - 1 donor atom;

Bidentate – 2 donor atoms; Polydentate - > 2 donor atoms;
Chelating agents – another name for bidentate or polydentate ligands

❑ Overall charge on the complex ion is determined by oxidation state

of the metal and charges on the ligands

Monodentate ligands: H2O, Cl-, OH-, CO, CN-, NH3, PPh3 etc.
 Coordination Complex: Ligands
❑ Bidentate Ligands:

❑ Tridentate Ligands:

Terpyridine
(terpy)

1,1,1-Tris(diphenylphosphinomethyl)ethane
(tdme) Diethylenetriamine
(Dien or DETA)
 Coordination Complex
macrocyclic ligands

Coord. Chem. Rev., 254, 2010, 1686-1712

 Werner’s Theory
❑ A chemical mystery: Same metal, same ligands, different number of
ions when dissolved

❑ In 1823, Werner proposed a theory to describe the structure and formation of

coordination compounds. It is because of this theory that he got the Nobel prize
and is known as the father of coordination chemistry.
The important postulates of Werner’s theory are:
❑ The central metal in coordination compounds show two types of
valency. They are the primary and secondary valency.
❑ The primary valency relates to the oxidation state and the
secondary valency relates to the coordinate number.
 Werner’s Theory
❑ Werner’s theory is responsible for the formation of structures of various cobalt
amines.
❑ Cobalt has a primary valency (oxidation state) of three and exhibits secondary
valency (coordination number) of 6.
❑ Werner proposed putting all molecules and ions within the sphere in brackets and
those “free” anions (that dissociate from the complex ion when dissolved in
water) outside the brackets.

❑ Number of ions produced in solution per formula unit are different.

❑ Precipitation of AgCl will confirm the amount of free Cl–; this will indicate the
number of Cl– ions are directly connected to the Co+3.
 Oxidation number for the metal
❑ Knowing the charge on a complex ion and the charge on each
ligand, one can determine the oxidation number for the metal.

❑ Knowing the oxidation number on the metal and the charges on

the ligands, one can calculate the charge on the complex ion.
 Isomers
❑ Isomers have the same molecular formula, but their atoms are
arranged either in a different order (structural isomers) or spatial
arrangement (stereoisomers).
 Ionization Isomers
❑ Ionization Isomers: occur when a ligand that is bound to the metal
center exchanges places with an anion or neutral molecule that
was originally outside the coordination complex.

❑ The geometry of the central metal ion and the identity of other
ligands are identical.

❑ The ions generated by isomers are in solution are different.

[Co(NH3)5(SO4)]Br
vs.
[Co(NH3)5Br]SO4
 Hydrate Isomers
❑ It is a specific kind of ionization isomer where a water molecule
exchanges places between inside and outside the coordination
sphere.

❑ CrCl3.6H2O can generate three different compounds based on how

many water molecule directly binds to the Cr+3 center.
❑[CrCl2(H2O)4]Cl.2H2O
❑[CrCl(H2O)5]Cl2.H2O
❑[Cr(H2O)6]Cl3

❑ The dotted water molecules are part of the lattice; they existed in
crystalline frameworks

❑ Reactivities of these complexes are different. Think about

reaction with AgNO3.
 Coordination Isomers
❑ Occurred in coordination compounds in which the
cations and anions are complex ions.

❑ Composition of the complex ion differs.

❑ Coordination number of the metals remains the same,

but the ligands attached to a specific metal ion change.

❑ [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]

❑ [Zn(NH3)4][Cu(Cl)4] and [Cu(NH3)4][Zn(Cl)4]

 Linkage Isomers
❑ Composition of the complexes is same; only difference is the donor
atom of the ligands which will bind to the central metal ions.

❑ Generally observed with complexes having ambidentate ligands such

as
❑ thiocyanate, (M-SCN) vs isothiocyanate, (M-NCS)
❑ nitrite, NO2−
❑ sulfite, SO32−
❑ Dimethyl sulfoxide (DMSO)
 Geometric Isomers
❑ Geometric Isomers: Coordination compounds having same set of
ligands, but their spatial arrangement is different.
❑ Most common in square planar and octahedral complexes.
❑ For a tetrahedral complex, geometric isomerism is not possible (all
possible structures are equivalent).
❑ Square Planar: Compound type No. of isomers
Ma2b2 2
Mabcd 3
❑ a, b, c, and d are monodentate
ligands
 Geometric Isomers: Octahedral Isomers
❑ Octahedral complexes (MA5B) in which only one ligand is different from the other
five: only one structure is possible

MA4B2: two isomers are possible

https://chem.libretexts.org/
 MA3B3 : facial and meridional isomers
❑ fac-isomers: three identical ligands occupies one face of the
octahedron
❑ mer-isomers: three identical ligands occupies a plane passing through
the metal atom

fac-[CoCl3(NH3)3] https://chem.libretexts.org/ mer-[CoCl3(NH3)3]

 M(AA)2B2
❑ M(AA)2B2: AA is a bidentate ligand; three stereoisomers (2 cis- and 1
trans- are possible.
❑ Example [Co(en)2Cl2]+
Ethylenediamine (en)

Mirror plane Mirror plane

trans-
cis-
Non-superimposable mirror images Superimposable mirror images

❑ cis- isomer of MAA2b2 may also exhibit optical isomerism

 Optical Isomers
❑Optical isomers will have different spatial arrangements of the
atoms and have non-superimposable mirror images.
❑Each non-superimposable mirror image structure is called an
enantiomer. Molecules or ions that exist as optical isomers are
called chiral.
❑They differ in the direction with which they rotate plane-polarized
light. These are possible for both tetrahedral and octahedral
complexes, but not square planar.

❑Co(en)3]3+ have
two optical
isomers which
are non-
superimposable
to each other
 Coordination Complex
❑Enantiomers do not have a plane of symmetry

has a plane
of symmetry
enantiomers

Optically inactive; has plane of symmetry

 Valence Bond Theory (VBT)
❑ In 1928, Linus Pauling (got Nobel Prize in 1954) combined Lewis's pair bonding
idea with the Heitler-London theory to propose valence bond theory. It was
developed to describe resonance and orbital hybridization.
❑ According to VBT, bonding is caused by the overlap of half-filled atomic orbitals.
The two atoms share each other's unpaired electron to form a filled orbital to
form a hybrid orbital and bond together.

❑ To explain the structures and magnetic properties of coordination complexes: VBT

utilizes hybridization of metal valence orbitals. (n-1)d, ns and np undergo
hybridization to give hybridized orbitals. An empty hybrid orbital on the metal
center can accept a pair of electrons from a ligand to form a σ-bond.
 Coordination Complex

Cr(CO)6 Ni(CO)4

Fe(CO)5
 Limitations of Valence Bond Theory

❑Does not explain the colour exhibited by the coordination

complexes.

❑Quantitative interpretation of magnetic data is not given.

❑ It can not exactly predict geometry of a complex having

coordination number four (will it be square planar or tetrahedral?).

❑Weak and strong ligands or high-spin and low-spin complexes

cannot be distinguished.

❑The thermodynamic and kinetic stabilities of complexes are not

quantitatively interpreted.
 Crystal Field Theory (CFT)
❑ Crystal field theory (CFT) was developed by physicists Hans Bethe
and John Hasbrouck van Vleck in the 1930s. Interestingly, both won
the Nobel Prize in Physics in 1967 and 1977 respectively.

❑ Origin of the name Crystal field theory: It was initially introduced to

explain the properties of the crystalline materials.
Basic Features of CFT
❑The ligands are considered as point charges.
❑The interaction between the metal ion and the ligand is presumed
to be electrostatic (ionic) in nature. In ideal CFT, no covalent
interaction between the metal and ligands is considered.
❑Electrostatic perturbation of the metal electron (e.g. d-orbital
electron) by the ligands.
❑Effect on the energy and degeneracy of the metal orbitals.
 d-Orbitals
Nodal plane is a plane with the
probability of finding an electron is zero.

❑ The phase of the wave function for the different lobes is indicated by color: orange for
positive and blue for negative.
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 Splitting of the metal d-orbital: Linear Field
❑ Consider the ligands are approaching along
the ±Z direction.
❑ Metal orbitals having lobes along the ±Z
direction will be more affected (more
repulsion).
Energy

❑ Degeneracy will be destroyed.

❑ Metal orbitals having the Z component Barycentre: centre of gravity

will be higher in energy compare to will be the same before and
others. after splitting of the orbitals

❑ Think about what will happen with the p-orbitals under this linear
ligand filed.
 d-Orbitals: Octahedral Field
❑ The corners of octahedron
are assumed to be placed
on the axes.

❑ The ligands approach along

the axes and occupy the
corners

❑ Electrons in the d orbitals

lying along the axes are
repelled the most, while
those lying in between the
axes are less repelled.
d-Orbitals: Octahedral Field
 CFT in an Octahedral (Oh) Field
❑ The energy separation between the
two levels is denoted by Δo or 10 Dq.
❑ The higher energy set of orbitals (dz2
and dx2-y2) are labeled as eg and the
lower energy set is labeled as t2g.

❑ To maintain the average energy, the eg

orbitals need to be destabilized by 0.6
Δo (6 Dq) and the t2g orbitals to be
stabilized to the extent of 0.4 Δo (4 Dq)
g = gerade; symmetric with respect to center of inversion
u = ungerade; antisymmetric w.r.t. center of inversion
t2g: triply degenerate set of orbitals; eg: doubly degenerate set of orbitals

❑ Metal center lies at the center of inversion in an octahedral complex having 6

identical ligands.
❑ p-orbitals: signs of the lobes changes on inversion in Oh-filed; hence they are
ungerade.
❑ What will be for s-orbital?
CFT in an Octahedral Field: Summery

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