Crystal Field Theory

Factors That Affect the Magnitude of o

Nature of the ligands
For a series of chem similar ligands,
magnitude of o decreases
as size of donor atom increases
 Factors That Affect the Magnitude of o
Nature of the ligands
because smaller, more localized charges
interact
 Nature of the ligands
experimentally observed order of
the crystal field splitting energies
produced by different ligands is called:
the spectrochemical series
 Nature of the ligands

1. Strong-field ligands interact strongly

with d orbitals of metal ions
and give a large o

2. Weak-field ligands interact

more weakly and give a smaller o
 The Spectrochemical Series
splitting of d orbitals in crystal field model
not only depends on geometry of the complex

also depends on nature of the metal ion,

charge on this ion,
and the ligands that surround the metal.
 The Spectrochemical Series

When geometry and ligands are held constant,

this splitting decreases in the following order:

Pt4+ > Ir3+ > Rh3+ > Co3+ > Cr3+ > Fe3+ > Fe2+ > Co2+ > Ni2+ > Mn2+

strong-field ions weak-field ions

Metal ions at one end are called strong-field ions,

because splitting due to crystal field is
unusually strong.
Ions at other end are known as weak-field ions.
 The Spectrochemical Series
When geometry & the metal are held constant,
splitting of d orbitals decreases in the following order:

CO CN- > NO2- > NH3 > -NCS- > H2O > OH- F- -SCN- Cl- > Br-

strong-field
weak-field ligands
ligands

Strong Field Ligands:

(strongest) CN−, CO > NO2− > en > NH3
Weak Field Ligands:
H2O > ox > OH− > F− > SCN−, Cl− > Br− > I− (weakest)
 tetrahedral crystal field:
imagine 3 ligands lying at alternating corners of a cube
The dx2-y2 & dz2 orbitals
on metal ion at center of the cube
lie between the ligands,
and dxy, dxz, & dyz orbitals point toward the ligands.
 Tetrahedral Complexes
Splitting of energies of orbitals in tetrahedral
complex, o, is smaller than in an octahedral
complex for two reasons:

1. d orbitals interact less strongly with ligands

in a tetrahedral arrangement.

2. Only four negative charges rather than six,

which decreases electrostatic
interactions
 tetrahedral crystal field:

the splitting observed in a tetrahedral crystal field is

opposite of splitting in octahedral complex.
 With square planar splittings,
energy level for the x2-y2 orbital is very high
so this is an especially good geometry
for d8 complexes, e.g. Pt(II), Ni(II), Pd(II), Au(III)
 Factors That Affect the Magnitude of o
Charge on the metal ion
Increasing charge on a metal ion has 2 effects:
1. Radius of metal ion decreases
2. Neg charged ligands are more strongly attracted
to it.

Both factors decrease metal-ligand distance,

which causes (-) charged ligands
to interact more strongly with the d orbitals.

magnitude of o increases
as charge on metal ion increases
Factors That Affect the Magnitude of o

Principal quantum # of the metal

For a series of complexes of metals

from same group in periodic table
with same charge and same ligands:

magnitude of o increases with

increasing quantum #:
 Factors That Affect the Magnitude of o
Principal quantum # of the metal
o (3d) << o (4d) < o (5d)

Increase in o w/ increasing principal quantum #

is due to: larger radius of valence orbitals
going down a column.

Repulsive ligand-ligand interactions

are important for smaller metal ions,
which results in shorter M–L distances
and stronger d-orbital-ligand interactions
 Colors of Transition-Metal Complexes
Striking colors exhibited by transition-metal complexes
are caused by the excitation of an e- from
a lower-lying d orbital to
a higher-energy d orbital,
which is called a d-d transition