CY1040: Chemical Bonding and Transition Metal Complexes
CHEMICAL BONDING
AND TRANSITION METAL COMPLEXES
TOPICS :-
● Bonding in transition metal complexes
● Coordination compounds
● Crystal field theory - Octahedral, tetrahedral and square planar complexes
● Crystal field stabilization energy
● Jahn-Teller Theorem
● Spectral, electronic and magnetic properties of coordination complexes
BONDING IN TRANSITION METAL COMPLEXES
There are three theories of metal to ligand bonding in complexes, all dating
back to the 1930s.
1. Valence bond theory
2. Crystal field theory
3. Molecular orbital theory
1. VALENCE BOND THEORY
● Proposed by Linus Pauling in 1931.
● Bonding occurs between metal and ligands.
● Vacant valence orbitals (s, p, d) of the metal atom hybridize to give
rise to same number of hybrid orbitals.
● The hybrid orbitals are directed towards the ligands according to the
geometry of the complex.
● Filled ligand orbital having a pair of electrons overlap with a vacant
hybrid orbital of the metal.
● Vacant hybrid orbitals of the metal atom/ion overlaps with the filled
orbital of the ligand.
● Coordinate covalent bond is formed.
● The bonding is considered to be purely covalent.
● Total number of orbitals of the metal atom/ ion which undergo hybridization is equal
to the coordination number of the central metal atom/ion.
● The d - orbitals involved in hybridization can be either inner (n-1)d orbitals (d2sp3) or
the outer n-d orbitals (sp3d2) in case of octahedral complexes and are called as low
spin and high spin complexes respectively.
● Tetrahedral complexes have sp3 hybridization.
● Square planar complexes have dsp2 hybridization.
● Knowing the magnetic properties of complexes, number of unpaired electrons,
hybridization (inner or outer sphere), shape and stability of complexes can be
predicted.
Example for Square planar complex
Example for Tetrahedral complex
Example for Octahedral complex
Example for Octahedral complex
Limitations of valence bond theory
● Only provides qualitative explanation.
● Does not explain the colour and electronic spectra of complexes.
● Fails to explain why a metal ion in a particular oxidation state form
low spin & high spin complexes.
● E.g. : Co3+ form complexes [Co(NH3)6]3+ and [CoF6]3- , the former is low
spin and the latter is high spin.
Limitations of valence bond theory
● Does not predict the relative stability of the complexes.
● Fails to explain why some complexes are labile and others inert.
● Labile complexes are those in which one or more ligands are easily
displaced by some other ligand.
● Inert complexes are those in which displacement of ligand from the
complexes is very slow / difficult.
● Does not take into account the splitting of d- orbitals.
Limitations of valence bond theory
● Does not explain the variation of magnetic moment with temperature.
● Fails to explain the difference between measured & calculated
magnetic moment.
● Does not predict whether the complexes having coordination number
4 will have tetrahedral or square planar geometry (eg:- VBT considers
Ni(acac)2 to have tetrahedral geometry , actually it has octahedral
geometry).
2. CRYSTAL FIELD THEORY
● This theory was first proposed in 1929 by Hans Bethe.
● It has been very successful in explaining the electronic spectra and
magnetism of transition metal complexes.
● Main difference from VBT is that in CFT , bond between metal and ligands
is considered to be purely electrostatic.
● If the ligands are –vely charged ( CN-, Br- etc.), the interaction between
metal and ligand is called ion-ion interactions.
● If the ligands are neutral (like CO, NH3 , H2O) , the interaction between
metal and ligand is called ion-dipole interactions.
Assumptions of crystal field theory
● Central metal atom / ion is surrounded by a number of ligands.
● Ligands are considered as point charges.
● Point charges are electric charges that exist as single point. They do not
have volume or area.
● If the ligands have –ve charge , the interaction between the central metal
atom/ion and the ligands is 100% ionic.
● If the ligands are neutral, the negative end of the dipole of the ligand is
oriented towards the central metal atom/ion , resulting in electrostatic
interaction.
Assumptions of crystal field theory
● For a isolated metal atom / ion , all the five d- orbitals have the same
energy. (Degenerate Orbitals).
● As ligands approach the central metal atom/ion, the electrons in the metal
orbitals will experience repulsion due to lone pair of electrons of the
ligand.
● Due to different shapes and orientation of the d - orbitals, the repulsions
experienced by the d – orbitals will be different.
● Orbitals lying in the direction of the ligands will experience greater
repulsion & their energies will increase more.
Assumptions of crystal field theory
● Orbitals lying away from the direction of approach of the ligands will
experience lesser repulsion & their energies will be raised to a lesser
extent.
● So, the d- orbitals of the central metal atom/ion are split up due to
electric field of the ligands.
● The splitting of five d- orbitals of central atom/ion into two sets of
orbitals having different energies in the presence of electric field of
the ligands is called Crystal Field Splitting.
Assumptions of crystal field theory
● The variation in the number of ligands around the central metal
atom/ion will affect the relative energies of d-orbitals differently.
● Crystal field splitting of the d-orbitals will be different for different
coordination numbers and geometries.
● Magnetic properties, colour of the compounds , electronic spectra and
preference for a particular geometry can be explained by CFT.
Shape of five d orbitals
Splitting in octahedral complexes
Splitting in tetrahedral complexes
Splitting in square planar complexes
CRYSTAL FIELD STABILIZATION ENERGY (CFSE)
The difference in the amount of energy on filling of electrons in the split d-
orbitals , is known as CFSE.
For Oh complexes, let us consider a dp+q ion with p electrons in t2g and q
electrons in eg orbitals, then from the CFT splitting diagram we can write,
CFSE = [-0.4p + 0.6q] ∆o + mP
P be the mean pairing energy which is the energy required to pair two
electrons against electron-electron repulsion in the same orbital.
m = number of electron pairs, then for octahedral complexes
● Similarly for Td complexes,
CFSE = [0.4p - 0.6q] ∆t + mP
Δt ~ 4/9 Δo (If the ligands are same)
● Td complexes are almost invariably high-spin
When Td complexes are favoured over Oh?
❖ Ligands are large and bulky.
❖ Ligands are weak field, and the loss in CFSE is thus less important.
❖ The central metal has a low oxidation state.
❖ Metal with no CFSE (d0, d5 or d10).
❖ M-Cl/Br/I complexes form tetrahedral structures.
Factors Affecting the Magnitude of Δo:
❖ Nature of the ligands.
❖ Number and geometry of the ligand
❖ Oxidation state/charge of the metal ion.
❖ Nature of the metal ion.
Factors Affecting the Magnitude of Δo:
❖ Nature of the ligands
● Ligands which cause only a small degree of
crystal field splitting are termed weak field
ligands.
● Ligands which cause a large splitting are
called strong field ligands.
● Most Δ are in the range 7000 to 30000 cm−1.
The anionic ligands (X-) are expected to show greater repulsion than the neutral ligands (CO, CN-)-Limitation.
Factors Affecting the Magnitude of Δo:
❖ Number and geometry of the ligand
The magnitude of splitting (Δo) is high for the six-coordinated octahedral
complexes than the four coordinated tetrahedral complexes.
Factors Affecting the Magnitude of Δo:
❖ Effect of the charge on the metal ion on Δo
The magnitude of splitting (Δo) increases as the charge on the metal ion
increases.
Factors Affecting the Magnitude of Δo:
Nature of the metal ion
● Splitting trend: 3d<4d<5d
● 3d metals are less diffused than 4d and 5d and thus less interaction/repulsion.
JAHN TELLER THEOREM
The Jahn-Teller theorem states that any non-linear molecule in a degenerate electronic
state will undergo a distortion that lowers its symmetry and energy, removing the
degeneracy.
Or, to put in a different way, when a degenerate set of orbital is occupied asymmetrically
then a distortion will occur which will remove the degeneracy of the orbital.
If the d electrons are asymmetrically arranged, they will repel some ligands in the
complex more than others.
Thus, the structure is distorted because some ligands are prevented from approaching
the metal as closely as others.
JAHN TELLER THEOREM
The eg orbitals point directly at the ligands. Thus, asymmetric filling of the eg orbitals results in
some ligands being repelled more than others. This causes a significant distortion of the
octahedral shape.
In contrast, the t2g orbitals do not point directly at the ligands but point in between the ligand
directions. Thus, asymmetric filling of the t2g orbitals has only a very small effect on the
geometry.
JAHN TELLER THEOREM
● If the ligand is present in Z-axis or axial axis, it will expand and bond length is
increased when moved toward outside is called Z-out distortion and the reverse is
called Z-in distortion.
JAHN TELLER THEOREM
● In z-out distortion, the repulsion between electrons in ligand orbital and metal orbital
is decreased due to elongation of z-axis. So the dz2 orbital is lower in energy and
also dxz, dyz.
● For z-in distortion the repulsion between of electrons in ligand orbital and metal
orbital is increased as they come closer to each other. So the dz2 orbital is higher in
energy.
● The lower the energy more stable the complex.
JAHN TELLER THEOREM
SPECTRAL PROPERTIES OF COMPLEXES - COLOUR
● When atoms or molecules absorb light at the proper frequency, their electrons are
excited to higher-energy orbitals.
● For many main group atoms and molecules, the absorbed photons are in the ultraviolet
range of the electromagnetic spectrum, which cannot be detected by the human eye.
● For coordination compounds, the energy difference between the d orbitals often allows
photons in the visible range to be absorbed.
SPECTRAL PROPERTIES OF COMPLEXES - COLOUR
● The human eye perceives a mixture of all the colors, in the proportions present in
sunlight, as white light.
● Complementary colors, those located across from each other on a color wheel, are
also used in color vision.
● The eye perceives a mixture of two complementary colors, in the proper
proportions, as white light.
● Likewise, when a color is missing from white light, the eye sees its complement.
● For example, when red photons are absorbed from white light, the eyes see the
color green. When violet photons are removed from white light, the eyes see
lemon yellow.
● The blue color of the [Cu(NH3)4]2+ ion results because this ion absorbs orange and
red light, leaving the complementary colors of blue and green.
MAGNETIC PROPERTIES OF COMPLEXES
Many transition metal complexes contain unpaired electrons and are therefore paramagnetic.
In contrast, molecules like N₂ and ions such as Na⁺ and [Fe(CN)₆]⁴⁻, which have all electrons
paired, are diamagnetic. Diamagnetic substances are slightly repelled by magnetic fields.
The extent of paramagnetism in a compound is measured by its magnetic moment (μ). A larger
μ indicates stronger paramagnetism.
The magnetic moment (µ) is calculated using the spin-only formula:
Where:
● n = Number of unpaired electrons
● BM = Bohr Magneton
MAGNETIC PROPERTIES OF COMPLEXES