Bonding in Coordination Compounds: Crystal Field Theory: Boundless Chemistry

Boundless Chemistry
Transition Metals
Bonding in Coordination Compounds: Crystal Field

Theory
https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

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Crystal Field Theory
Crystal field theory states that d or f orbital degeneracy can be broken by the electric
field produced by ligands, stabilizing the complex.
LEARNING OBJECTIVES
Discuss the relationships between ligand binding in a metal complex and the
degeneracy of the d orbitals and between the geometry of a metal complex
and the splitting of the d orbitals.
KEY TAKEAWAYS
Key Points
When the ligands approach the central metal ion, d- or f-subshell

degeneracy is broken due to the static electric field.
Because electrons repel each other, the d electrons closer to the

ligands will have a higher energy than those further away, resulting in
the d orbitals splitting.
The crystal field stabilization energy (CFSE) is the stability that results
from ligand binding.
Key Terms
degenerate: Having the same quantum energy level.
ligand: An ion, molecule, or functional group that binds to another

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chemical entity to form a larger complex.
The Crystal Field Theory (CFT) is a model for the bonding interaction between transition
metals and ligands. It describes the effect of the attraction between the positive charge
of the metal cation and negative charge on the non-bonding electrons of the ligand.
When the ligands approach the central metal ion, the degeneracy of electronic orbital
states, usually d or f orbitals, are broken due to the static electric field produced by a
surrounding charge distribution. CFT successfully accounts for some magnetic
properties, colors, and hydration energies of transition metal complexes, but it does not
attempt to describe bonding.
The electrons in the d orbitals of the central metal ion and those in the ligand repel each
other due to repulsion between like charges. Therefore, the d electrons closer to the
ligands will have a higher energy than those further away, which results in the d orbitals
splitting in energy. This splitting is affected by:
the nature of the metal ion
the metal’s oxidation state (a higher oxidation state leads to a larger splitting)
the arrangement of the ligands around the metal ion
the nature of the ligands surrounding the metal ion
All of the d orbitals have four lobes of electron density, except for the dz2 orbital, which
has two opposing lobes and a doughnut of electron density around the middle. The d
orbitals can also be divided into two smaller sets. The dx2–y2 and dz2 all point directly
along the x, y, and z axes. They form an eg set. On the other hand, the lobes of the dxy,
dxz, and dyz all line up in the quadrants, with no electron density on the axes. These
three orbitals form the t2g set. In most cases, the d orbitals are degenerate, but
sometimes they can split, with the eg and t2g subsets having different energy. The CFT
accounts for this.

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d xy d yz d xz
d x 2-y 2 dz2
d orbitals: This gives an overview of the d orbitals. The central model shows the
combined d-orbitals on one set of axes.
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. For example, in the case of an octahedron, the t2g set becomes
lower in energy. As a result, if there are any electrons occupying these orbitals, the
metal ion is more stable in the ligand field by the amount known as the CFSE.
Conversely, the eg orbitals are higher in energy. So, putting electrons in them reduces
the amount of CFSE.

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Octahedral CFT splitting: Electron diagram
for octahedral d shell splitting.
Crystal field stabilization is applicable to the transition-metal complexes of all

geometries. The reason that many d8 complexes are square-planar is the very large
amount of crystal field stabilization that this geometry produces with this number of
electrons.
Square planar CFT splitting:

Electron diagram for square planer
d subshell splitting.
Octahedral Complexes
Octahedral complexes have six ligands symmetrically arranged around a central atom,

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defining the vertices of an octahedron.
LEARNING OBJECTIVES
Discuss the degeneracy of the d orbitals in an octahedral metal complex.
KEY TAKEAWAYS
Key Points
The term octahedral is used somewhat loosely by chemists, focusing

on the geometry of the bonds to the central atom and not considering
differences among the ligands themselves.
When two or more ligands are coordinated to an octahedral metal

center, the complex can exist as isomers.
In an octahedral complex, the d-subshell degeneracy is lifted.
Key Terms
degeneracy: Having the same quantum energy level.

vertex: The common point of the two rays of the angle, or its equivalent
structure in polyhedra (meeting of edges) and higher order polytopes.

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Octahedral molecular geometry describes the shape of compounds wherein six atoms
or groups of atoms or ligands are symmetrically arranged around a central atom. The
octahedron has eight faces, hence the prefix octa-. An example of an octahedral
compound is molybdenum hexacarbonyl (Mo(CO)6).
The term octahedral is used somewhat loosely by chemists, focusing on the geometry of
the bonds to the central atom and not considering differences among the ligands
themselves. For example, [Co(NH3)6]3+, which is not octahedral in the mathematical
sense due to the orientation of the N-H bonds, is referred to as octahedral.
When two or more types of ligands are

coordinated to an octahedral metal center,
the complex can exist as isomers. The
number of possible isomers can reach 30
for an octahedral complex with six
different ligands (in contrast, only two
stereoisomers are possible for a
tetrahedral complex with four different
ligands).
Hexamminecobalt(III) chloride: Example

For a free ion, such as gaseous Ni2+ or of an octahedral coordination complex.
Mo, the d orbitals are degenerate. In an
octahedral complex, this degeneracy is
lifted. The dz2 and dx2−y2 (the so-called eg set), which are aimed directly at the ligands,
are destabilized. On the other hand, the dxz, dxy, and dyz orbitals (the so-called t2g set)
see a decrease in energy.
Given that such a variety of octahedral complexes exist, it is not surprising that a wide
variety of reactions have been described. These reactions can be classified as follows:
Ligand substitution reactions (via a variety of mechanisms)

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Ligand addition reactions, including protonation (among many others)
Redox reactions (in which electrons are gained or lost)
Rearrangements where the relative stereochemistry of the ligands change within

the coordination sphere
Many reactions of octahedral transition metal complexes occur in water. For example,
[Co(NH3)5Cl]2+ slowly aquates to give [Co(NH3)5(H2O)]3+ in water, especially in the
presence of acid or base.
Tetrahedral and Square Planar Complexes
Both tetrahedral and square planar complexes have a central atom with four
substituents.
LEARNING OBJECTIVES
Discuss the d-orbital degeneracy of square planar and tetrahedral metal

complexes.
KEY TAKEAWAYS
Key Points
In tetrahedral molecular geometry, a central atom is located at the

center of four substituents, which form the corners of a tetrahedron.
Tetrahedral geometry is common for complexes where the metal has d0

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or d10 electron configuration.
The CFT diagram for tetrahedral complexes has dx2−y2 and dz2 orbitals
equally low in energy because they are between the ligand axis and
experience little repulsion.
In square planar molecular geometry, a central atom is surrounded by

constituent atoms, which form the corners of a square on the same
plane.
The square planar geometry is prevalent for transition metal complexes

with d8 configuration.
The CFT diagram for square planar complexes can be derived from
octahedral complexes yet the dx2-y2 level is the most destabilized and
is left unfilled.
Key Terms
substituents: Any atom, group, or radical substituted for another, or

entering a molecule in place of some other part which is removed.
degeneracy: Having the same quantum energy level.

Tetrahedral Complexes
In tetrahedral molecular geometry, a central atom is located at the center of four

substituent atoms, which form the corners of a tetrahedron. The bond angles are
approximately 109.5° when all four substituents are the same. This geometry is
widespread, particularly for complexes where the metal has d0 or d10 electron
configuration.

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For example,
tetrakis(triphenylphosphine)palladium(0),
a popular catalyst, and nickel carbonyl,
an intermediate in nickel purification, are
tetrahedral. Many complexes with
incompletely filled d-subshells are
tetrahedral as well—for example, the
tetrahalides of iron(II), cobalt(II), and
nickel(II).
Tetrahedral complexes have ligands in all

of the places that an octahedral complex
does not. Therefore, the crystal field
splitting diagram for tetrahedral Tetrakis(triphenylphosphine)palladium: 3-
dimensional representation of tetrahedral
complexes is the opposite of an Tetrakis(triphenylphosphine)palladium
octahedral diagram. The dx2−dy2 and dz2
orbitals should be equally low in energy

because they exist between the ligand axis,
allowing them to experience little repulsion.
In contrast, the dxy,dyz, and dxz axes lie
directly on top of where the ligands go. This
maximizes repulsion and raises energy
levels.
Nickel carbonyl: 2-dimensional

representation of tetrahedral nickel
carbonyl.

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image
Tetrahedral CFT splitting: Notice the energy splitting in the

tetrahedral arrangement is the opposite for the splitting in octahedral
arrangements.
Square Planar Complexes
In square planar molecular geometry, a central atom is surrounded by constituent atoms,

which form the corners of a square on the same plane. The geometry is prevalent for
transition metal complexes with d8 configuration. This includes Rh(I), Ir(I), Pd(II), Pt(II), and
Au(III). Notable examples include the anticancer drugs cisplatin [PtCl2(NH3)2] and
carboplatin.

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In principle, square planar geometry can be
achieved by flattening a tetrahedron. As such, the
interconversion of tetrahedral and square planar
geometries provides a pathway for the
isomerization of tetrahedral compounds. For
example, tetrahedral nickel(II) complexes such as
NiBr2(PPh3)2 undergo this change reversibly..
The
image removal
of a pair
of
ligands
from the
Carboplatin: 2- and 3-
z-axis of dimensional representations of
the anti-cancer drug carboplatin
an
octahedron leaves four ligands in the x-y

plane. Therefore, the crystal field splitting
diagram for square planar geometry can be
derived from the octahedral diagram. The
CFT energy diagram for square planar removal of the two ligands stabilizes the dz2
complexes: Notice how the dx2 – y2 level, leaving the dx2-y2 level as the most
orbital is unfilled.
destabilized. Consequently, the dx2-y2
remains unoccupied in complexes of metals
with the d8 configuration. These compounds typically have sixteen valence electrons
(eight from ligands, eight from the metal)
Color
Transition metal complexes are often colored due to either d-d or change band electron
transitions induced by the absorption of light.

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LEARNING OBJECTIVES
Discuss the process which provides color in coordination complexes.
KEY TAKEAWAYS
Key Points
The colors in metal complexes come from the d orbitals because they
are not involved in bonding.
d-d electron transitions are allowed in complexes if the center of

symmetry is disrupted, resulting in a vibronic transition.
In Metal-to- Ligand Charge Transfer (MLCT), electrons can be promoted

from a metal-based orbital into an empty ligand-based orbital.
An electron may jump from a predominantly ligand orbital to a

predominantly metal orbital (Ligand-to-Metal Charge Transfer or LMCT).
Coordination complex color results from the absorption of

complimentary colors.
Key Terms

band theory: In a solid, those ranges of energy that an electron is

allowed to have.
centrosymmetric: Having a center of symmetry.

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orbital: A specification of the energy and probability density of an
electron at any point in an atom or molecule.
Color in Coordination Compounds
Metal complexes often have spectacular colors caused by electronic transitions induced
by the absorption of light. For this reason, they are often applied as pigments. We know
that light can be emitted corresponding to the difference in energy levels. We could
expect them to come from the d-orbitals. This is because they are not involved in
bonding, since they do not overlap with the s and p orbitals of the ligands. Most
transitions that are related to colored metal complexes are either d–d transitions or
charge band transfer.
d-d Transitions
In a d–d transition, an electron in a d orbital on the metal is excited by a photon to

another d orbital of higher energy. In complexes of the transition metals, the d orbitals
do not all have the same energy. In centrosymmetric complexes, d-d transitions are
forbidden by the Laporte rule. The Laporte rule states that, if a molecule is
centrosymmetric, transitions within a given set of p or d orbitals are forbidden. However,
forbidden transitions are allowed if the center of symmetry is disrupted. Transitions that
occur as a result of an asymmetrical vibration of a molecule are called vibronic
transitions. Through such asymmetric vibrations, transitions that would theoretically be
forbidden, such as a d-d transition, are weakly allowed.
An example occurs in octahedral complexes such as in complexes of manganese(II). It

has a d5 configuration in which all five electrons have parallel spins. The color of such
complexes is much weaker than in complexes with spin-allowed transitions. In fact, many
compounds of manganese(II), like manganese(II) chloride, appear almost colorless.
Tetrahedral complexes have somewhat more intense color. This is because mixing d and

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p orbitals is possible when there is no center of symmetry. Therefore, transitions are not
pure d-d transitions.
Example of weaker color due to d-d transition: Sample of

manganese(II) chloride.
Change Band Transfer
Electrons can also be transferred between the orbitals of the metal and the ligands. In
Metal-to-Ligand Charge Transfer (MLCT), electrons can be promoted from a metal-based
orbital into an empty ligand-based orbital. These are most likely to occur when the metal
is in a low oxidation state and the ligand is easily reduced. Ligands that are easily
reduced include 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen), CO, CN-, and SCN-. An
example of color due to MLCT is tris(2,2′-bipyridyl)ruthenium(II), which is a versatile
photochemical redox reagent.

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Example of color due to MLCT transition: Sample of
tris(bipyridine)ruthenium(II)-chloride
Conversely, an electron may jump from a predominantly ligand orbital to a

predominantly metal orbital (Ligand-to-Metal Charge Transfer or LMCT). These can most
easily occur when the metal is in a high oxidation state. For example, the color of
chromate, dichromate, and permanganate ions is due to LMCT transitions.
“Seeing” Color
We can perceive colors for two reasons: either we see it because that color is the only
color not absorbed or because all colors of visible light are absorbed except for a
particular color known as its complimentary color.
Large energy differences should correspond to smaller wavelengths and purple colors,
while small energy differences should result in large wavelengths and colors closer to
red. For example, you might expect to see red for a complex with a small energy gap
and large wavelength. Green is the compliment of red, so complexes with a small energy
gap will actually appear green.

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The color we see for coordination complexes is a result of
absorption of complimentary colors. A decrease in the
wavelength of the complimentary color indicates the
energy gap is increasing and can be used to make general
rankings in the strengths of electric fields given off by
ligands. These phenomena can be observed with the aid
of electronic spectroscopy (also known as UV-Vis).
Magnetic Properties
Metal complexes that have unpaired electrons are

magnetic.
LEARNING OBJECTIVES
Discuss the correlation between the electronic

Examples of color due
structure of a coordination complex and its magnetic to LCMT transitions:
properties. Samples of (from top to
bottom) potassium
chromate, potassium
dichromate, and
potassium
permanganate.
KEY TAKEAWAYS
Key Points
Unpaired electrons exist when the complex has an odd number of

electrons or because electron pairing is destabilized.
The more unpaired electrons, the stronger the magnetic property.

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Tetrahedral complexes have weaker splitting because none of the
ligands lie within the plane of the orbitals.
Square planar compounds are always low-spin and therefore are

weakly magnetic.
In bi- and polymetallic complexes, the electrons may couple through

the ligands, resulting in a weak magnet, or they may enhance each
other.
Key Terms
diamagnetic: Exhibiting diamagnetism; repelled by a magnet.

chemical entity to form larger complex.
paramagnetic: Exhibiting paramagnetism (the tendency of magnetic

dipoles to align with an external magnetic field).
Magnetic Properties of Coordination Compounds
An interesting characteristic of transition metals is their ability to form magnets. Metal

complexes that have unpaired electrons are magnetic. Since the last electrons reside in
the d orbitals, this magnetism must be due to having unpaired d electrons. Considering
only monometallic complexes, unpaired electrons arise because the complex has an
odd number of electrons or because electron pairing is destabilized.
For example, monomeric Ti(III) species have one d electron and must be (para)magnetic,
regardless of the geometry or the nature of the ligands. Ti(II), with two d electrons, forms
some complexes that have two unpaired electrons and others with none.
As an example, Fe prefers to exist as Fe3+ and is known to have a coordination number

of six. Since the configuration of Fe3+ has five d electrons, we would expect to see five

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unpaired spins in complexes with Fe. This is true for [FeF6]3-; however, [Fe(CN)6]3- only
has one unpaired electron, making it a weaker magnet. This trend can be explained
based on the properties of the ligands. We expect CN− to have a stronger electric field
than that of F−, so the energy differences in the d orbitals should be greater for the
cyanide complex.
Crystal field theory splitting diagram: Example of influence of ligand electronic properties
on d orbital splitting. This shows the comparison of low-spin versus high-spin electrons.
In order for this to make sense, there must be some sort of energy benefit to having
paired spins for our cyanide complex. That is, the energy level difference must be more
than the repulsive energy of pairing electrons together. Since systems strive to achieve
the lowest energy possible, the electrons will pair up before they will move to the higher
orbitals. This is referred to as low spin, and an electron moving up before pairing is
known as high spin.
Tetrahedral complexes have naturally weaker splitting because none of the ligands lie
within the plane of the orbitals. As a result, they have either have too many or too few d
electrons to warrant worrying about high or low spin. Square planar compounds, on the
other hand, stem solely from transition metals with eight d electrons. [Ni(CN)4]2-,
[Pt(NH3)3Cl]+, and [PtCl4]2- are all diamagnetic.
Since this encompasses the full spectrum of ligand strength, we can conclude that
square planar compounds are always low spin and therefore are weakly magnetic. In bi-

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and polymetallic complexes, in which the individual centers have an odd number of
electrons or electrons are high-spin, the situation is more complicated.
If there is interaction between the two (or more) metal centers, the electrons may couple,
resulting in a weak magnet, or they may enhance each other. When there is no
interaction, the two (or more) individual metal centers behave as if in two separate
molecules.
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Bonding in Coordination Compounds: Crystal Field Theory: Boundless Chemistry

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Boundless Chemistry

Bonding in Coordination Compounds: Crystal Field

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

When the ligands approach the central metal ion, d- or f-subshell

Because electrons repel each other, the d electrons closer to the

degenerate: Having the same quantum energy level.

ligand: An ion, molecule, or functional group that binds to another

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

the nature of the metal ion

the arrangement of the ligands around the metal ion

the nature of the ligands surrounding the metal ion

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

Crystal field stabilization is applicable to the transition-metal complexes of all

Square planar CFT splitting:

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

Discuss the degeneracy of the d orbitals in an octahedral metal complex.

The term octahedral is used somewhat loosely by chemists, focusing

When two or more ligands are coordinated to an octahedral metal

In an octahedral complex, the d-subshell degeneracy is lifted.

degeneracy: Having the same quantum energy level.

ligand: An ion, molecule, or functional group that binds to another

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

When two or more types of ligands are

Hexamminecobalt(III) chloride: Example

Ligand substitution reactions (via a variety of mechanisms)

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

Redox reactions (in which electrons are gained or lost)

Rearrangements where the relative stereochemistry of the ligands change within

Tetrahedral and Square Planar Complexes

Discuss the d-orbital degeneracy of square planar and tetrahedral metal

In tetrahedral molecular geometry, a central atom is located at the

Tetrahedral geometry is common for complexes where the metal has d0

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

In square planar molecular geometry, a central atom is surrounded by

The square planar geometry is prevalent for transition metal complexes

substituents: Any atom, group, or radical substituted for another, or

degeneracy: Having the same quantum energy level.

ligand: An ion, molecule, or functional group that binds to another

In tetrahedral molecular geometry, a central atom is located at the center of four

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

Tetrahedral complexes have ligands in all

orbitals should be equally low in energy

Nickel carbonyl: 2-dimensional

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

Tetrahedral CFT splitting: Notice the energy splitting in the

Square Planar Complexes

In square planar molecular geometry, a central atom is surrounded by constituent atoms,

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

octahedron leaves four ligands in the x-y

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

Discuss the process which provides color in coordination complexes.

d-d electron transitions are allowed in complexes if the center of

In Metal-to- Ligand Charge Transfer (MLCT), electrons can be promoted

An electron may jump from a predominantly ligand orbital to a

Coordination complex color results from the absorption of

ligand: An ion, molecule, or functional group that binds to another

band theory: In a solid, those ranges of energy that an electron is

centrosymmetric: Having a center of symmetry.

https://courses.lumenlearning.com/boundless-chemistry/chapter/bonding-in-coordination-compounds-crystal-field-theory/ 04/11/2018, 14?46

Color in Coordination Compounds

In a d–d transition, an electron in a d orbital on the metal is excited by a photon to