CRYSTAL FIELD THEORY (CFT)

PRESENTATION BY:
Mr. SHAFI UR REHMAN
OUTLINE
• Introduction
• What is CFT
• Ligands
• Overview
• Splitting of d-orbital
• High and low spin
• CFT in octahedral complexes
• CFT in tetrahedral complexes
• CFT energy stabilization
INTRODUCTION
• CFT was proposed by the physicist Hans Bethe in 1929. Subsequent modifications were
proposed by J. H. Van Vleck in 1935 to allow for some covalency in the interactions.

• Crystal Field Theory was developed to describe important properties of complexes

(magnetism, absorption spectra, oxidation states, coordination,). The basis of the model is
the interaction of d-orbitals of a central atom with ligands, which are considered as point
charges.

• According to CFT, the attraction between the central metal and ligands in a complex is
purely electrostatic.
WHAT IS CFT
Crystal field theory describes

“The net change in crystal energy resulting from the orientation of d orbitals of a
transition metal cation inside a coordinating group of anions also called ligands.”

• A major feature of transition metals is their tendency to form complexes. A complex may be
considered as consisting of a central metal atom or ion surrounded by a number of ligands.
The interaction between these ligands with the central metal atom or ion is subject to crystal
field theory.
LIGANDS
• Ligands are ions or neutral molecules that bond to a central metal atom or ion. Ligands act as
Lewis bases (electron pair donors), and the central atom acts as a Lewis acid (electron pair
acceptor). Ligands have at least one donor atom with an electron pair used to form covalent
bonds with the central atom.
• The term ligand come from the latin word ligare, which meaning to bind) was first used by
Alfred Stock in 1916 in relation to silicon chemistry. Ligands can be anions, cations, or
neutral molecules. Ligands can be further characterized as monodentate, bidentate, tridentate
etc. A monodentate ligand has only one donor atom used to bond to the central metal atom or
ion.
• Examples for anionic ligands are F–, Cl–, Br–, I–, S2–, CN–, NCS–, OH–, NH2– and
neutral ligands are NH3, H2O, NO, CO.

• Lewis base which donates two lone pairs of electrons to the central metal atom is known as
bidentate ligands. They are often referred to as a “chelating ligands”. The complex which
contains chelating ligands is called “Chelates”.
OVERVIEW OF CFT
• In order to understand clearly the crystal field interactions in transition metal complexes, it
is necessary to have knowledge of the geometrical or spatial disposition of d orbitals. The
d-orbitals are fivefold degenerate in a free gaseous metal ion. If a spherically symmetric
field of negative ligand filed charge is imposed on a central metal ion, the d-orbitals will
remain degenerate but followed by some changes in the energy of free ion.

• Crystal field theory was proposed which described the metal-ligand bond as an ionic bond
arising purely from the electrostatic interactions between the metal ions and ligands. Crystal
field theory considers anions as point charges and neutral molecules as dipoles.
• When transition metals are not bonded to any ligand, their d orbitals are degenerate that is
they have the same energy. When they start bonding with other ligands, due to different
symmetries of the d orbitals and the inductive effect of the ligands on the electrons, the d
orbitals split apart and become non-degenerate.
SPLITTING OF D ORBITAL

• The splitting of d orbitals in the crystal field model not only depends on the geometry of the
complex, it also depends on the nature of the metal ion, the charge on this ion, and the
ligands that surround the metal. When the geometry and the ligands are held constant, this
splitting decreases in the following order.
• Metal ions at one end of this continuum are called strong-field ions, because the splitting
due to the crystal field is unusually strong. Ions at the other end are known as weak-field
ions.

• When the geometry and the metal are held constant, the splitting of the d orbitals decreases
in the following order.
HIGH AND LOW SPIN
• The complexion with the greater number of unpaired electrons is known as the high spin
complex, the low spin complex contains the lesser number of unpaired electrons. High spin
complexes are expected with weak field ligands whereas the crystal field splitting energy is
small Δ. The opposite applies to the low spin complexes in which strong field ligands cause
maximum pairing of electrons in the set of three t2 atomic orbitals due to large Δo.

• High spin – Maximum number of unpaired electrons.

• Low spin – Minimum number of paired electrons.
• Example: [Co(CN)6]3- & [CoF6]3-

• [Co(CN)6]3- – Low spin complex

• [CoF6]3- – High spin complex
CF SPLITTING IN OCTAHEDRAL COMPLEXES
• In the case of an octahedral coordination compound having six ligands surrounding the
metal atom/ion, we observe repulsion between the electrons in d orbitals and ligand
electrons.

• This repulsion is experienced more in the case of dx2-y2 and dz2 orbitals as they point
towards the axes along the direction of the ligand.

• Hence, they have higher energy than average energy in the spherical crystal field.

• On the other hand, dxy, dyz, and dxz orbitals experience lower repulsions as they are
directed between the axes.
• Hence, these three orbitals have less energy than the average energy in the spherical crystal
field.

• Thus, the repulsions in octahedral coordination compound yield two energy levels:
t2g– set of three orbitals (dxy, dyz and dxz) with lower energy
e.g – set of two orbitals (dx2-y2 and dz2) with higher energy
• This splitting of degenerate level in the presence of ligand is known as crystal field splitting.
The difference between the energy of t2g and eg level is denoted by “Δo” (subscript o stands
for octahedral.
CRYSTAL FIELD SPLITTING IN TETRAHEDRAL COMPLEX
• The splitting of fivefold degenerate d orbitals of the metal ion into two levels in a tetrahedral
crystal field is the representation of two sets of orbitals as Td. The electrons in dx2-y2 and
dz2 orbitals are less repelled by the ligands than the electrons present in dxy, dyz, and dxz
orbitals. As a result, the energy of dxy, dyz, and dxz orbital set are raised while that os the
dx2-y2 and dz2 orbitals are lowered.
• There are only four ligands in Td complexes and therefore the total negative charge of four
ligands and hence the ligand field is less than that of six ligands.
• The direction of the orbitals does not coincide with the directions of the ligands approach to
the metal ion.
• Thus, the repulsions in tetrahedral coordination compound yield two energy levels:

• t2– set of three orbitals (dxy, dyz and dxz) with higher energy

• e – set of two orbitals (dx2-y2 and dz2) with lower energy

• The crystal field splitting in a tetrahedral complex is intrinsically smaller in an octahedral
filed because there are only two thirds as many ligands and they have a less direct effect of
the d orbitals. The relative stabilizing effect of e set will be -6Dq and the destabilizing effect
of t2 set will be +4Dq
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, some of them become lower in energy
than before with respect to a spherical field known as the bari-center 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 bari centre.
• Owing to the splitting of the d orbitals in a complex, the system gains an extra stability due
to the rearrangement of the d electrons filling in the d levels of lower energy. The
consequent gain in bonding energy is known as crystal field stabilization energy (CFSE).

• If the splitting of the d-orbitals in an octahedral field is Δoct, the three t2g orbitals are
stabilized relative to the bari centre by 2/5 Δoct, and the eg orbitals are destabilized by 3/5
Δo.