CHM102A: General Chemistry

Inorganic Chemistry: Lecture 2

Sabuj Kundu
sabuj@iitk.ac.in
d-orbitals

❑dxy: lobes lie in-between the x and the y axes.

❑dxz: lobes lie in-between the x and the z axes.
❑dyz: lobes lie in-between the y and the z axes.
❑dx2-y2: lobes lie on the x and y axes.
❑dz2: there are two lobes on the z axes and there is a donut shape ring
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 CFT in Tetrahedral Field

Ligands occupying the alternating

corners of a cube.

❑ The higher energy set of orbitals (dxz, dyz, dxy) are labeled as t2 and
the lower energy set (dz2 and dx2-y2) is labeled as e.
❑ The crystal field splitting in the tetrahedral field is intrinsically smaller
than in the octahedral field.
❑ For most purposes the relationship may be represented as Δt = 4/9 Δo
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 CFT in Tetrahedral Field
❑No orbitals directly
pointing toward the
ligands.

❑The e orbitals point

between the two ligands
present at opposite
corners of a cube (thereby
being less effected than
the t2 orbitals).

❑The t2 orbitals lie half an

edge of the cube from
ligand and point more
directly toward ligands
(destabilized). 4
http://faculty.uml.edu/ndeluca/84.334/topics/topic6.htm
Comparison of Octahedral and Tetrahedral Fields

Δt = 4/9 Δo

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 Determination of Δ
❑ Crystal filed splitting parameter (Δ) is generally measured by
electronic spectra.
❑ Let's look at this for [Ti(H2O)6]3+, it is a d1 complex.
❑ Electron in the t2g orbitals
absorb energy in the and gets
promoted to the eg orbitals to
show it’s purple color.

❑ The maximum of the absorption peak is at 493 nm (=

20,300 cm-1 = 243 kJ/mol). Hence, Δo for this complex is
20,300 cm-1 or 243 kJ/mol. Following E= h = hc/
equation.
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Factors Influencing the Δ

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 Factors Influencing the Δ
❑ Geometry of the complex: Tetrahedral complexes (ML4) have
smaller Δ than octahedral ones (ML6).
Δ = 10,200 cm-1 for [CoII(NH3)6]2+
5,900 cm-1 for [CoII(NH3)4]2+
❑ Oxidation states of the metal: Complexes having metal in higher
oxidation state will have larger Δ.

❑ Higher charge on the metal ion, pulls the ligands closer hence higher
electrostatic repulsion which results in larger splitting of d-orbitals.

Δ = 10,200 cm-1 for [CoII(NH3)6]2+ and 22,870 cm-1 for [CoIII(NH3)6]3+

Δ = 32,200 cm-1 for [FeII(CN)6]4- and 35,000 cm-1 for [FeIII(CN)6]3-

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 Factors Influencing the Δ
❑Larger and heavier metals in a same group have higher Δ.
For hexaamine complexes: Group 9
[MIII(NH3)6]3+: Δ = 22,870 cm-1 (Co)
34,100 cm-1 (Rh)
41,200 cm-1 (Ir)
❑ Larger size of 4d and 5d orbitals results in stronger interactions
with ligands.

❑ In d-block elements, in moving down in a group, the effective

nuclear charge on the metal gradually increases because of low
screening d- and f- orbital electrons.

❑ For larger metal ion, the ligands experience less steric crowding
and hence they can approach closer. Thus results in stronger
interaction and larger crystal field splitting. 9
 Factors Influencing the Δ
❑Nature of the ligands (Ligand filed strength) have
significant effect on Δ.
For [CoIIIL6]: Δ in cm-1: 13,100 (F-); 20,760 (H2O); 22,870 (NH3)
For [CrIIIL6]: Δ in cm-1: 15,060 (F-); 17,400 (H2O); 26,600 (CN-)

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 Spectrochemical Series
❑ An arrangement of ligands according to their ability to split the d-
orbitals or crystal field splitting parameter (Δ).
❑ It is based on the strength of ligands interaction with metal ions. It is
often listed, from weaker to stronger ligands

Weak Field I-  Br- S2- SCN- Cl- NO3- F-  C2O42-

H2O NCS- CH3CN < py  NH3 en  bipy phen
NO2- PPh3 CN- CO Strong Field
py = pyridine; en = ethylenediamine; bipy = 2,2'-bipyridine;
phen = 1,10-phenanthroline

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 Explanation of Spectrochemical Series using CFT
❑ It is not possible to explain every aspect of the spectrochemical
series using the basic postulates of CFT.
❑ Anionic vs Neutral Ligand: Anionic ligands are expected to interact
electrostatically more strongly than neutral ligands. However, many
anionic ligands (Br-, Cl-, F- etc.) are relatively weak than neutral CO,
Phen etc.
❑ Look at H2O vs OH- (neutral H2O is stronger ligand than OH-).

❑ I-  Br- Cl- F- (Ligand Field strength)

❑ Among them, the fluoride ion is the smallest and its charge density
is highest.
❑ It can approach much closer to the metal ion thereby increase the
electronic repulsion which leads to higher Δ.

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 Explanation of Spectrochemical Series using CFT
❑ I-  Br- Cl- F- (Ligand Field strength) : Fluoride ion can
approach much closer to the metal ion thereby increase the
electronic repulsion which leads to higher Δ.

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 F-  OH- O2- H2O
❑ To understand this, we have to look into the bonding modes between
these ligands with the metal.

❑ All ligands are “σ donors”. Other than the σ donation, some ligands (NOT
all) can have additional orbitals that can interact with other orbitals on the
metal. Ligand Field Theory (LFT) and Molecular Orbital Theory (MOT) can
properly explain this phenomenon.
❑ F- , OH- , O2- can rehybridize and donate a pair of electrons from their p-
orbitals to d-orbitals on the metal and form a π-bond.

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 F-  OH- O2- H2O
❑ F- , OH- , O2- can rehybridize and donate a pair of electrons from their
p-orbitals to d-orbitals on the metal and form a π-bond.
❑ This reduces the negative charge on the ligands and the positive
charge on the metal, hence Δo decreases.

O2- act as both a σ-donor and a π-donor

❑ Water acts only as a -donor ligand.

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 Why PPh3, CN-, CO are strong field ligands?
❑ CO or cyanide donates its sigma (nonbonding) electrons to the
metal, while accepting electron density from the metal through
overlap of a metal t2g orbital and a ligand π* orbital.
❑ This situation is called "back-bonding" because the ligand donates
σ-electron density to the metal and the metal donates π-electron
density to the ligand.
❑ The ligand is thus acting as a σ-donor and a π-acceptor.

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 Why PPh3, CN-, CO are strong field ligands?
❑ PPh3: σ-donor and a π-acceptor ligand.
❑ It can accept electrons from filled metal d-orbital to empty d-
orbital of P (and σ-* of P-Ph bond) (π-back bonding).

❑ To stabilize low oxidation states of metal, ligands which can

simultaneously bind the metal center and also withdraw electron
density from it are most suitable.

❑ Although, all the ligands are σ donors; in general: π donor< weak π

donor<σ only< π acceptor
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 Pairing Energy, P
❑ Pairing energy is needed in order to force an electron to fill an orbital that is
already occupied with an electron. The electrons can also fill higher energy orbitals
and avoid the pairing energy.
❑ The pairing energy, P, depends only on the metal not on the ligands. It consist of
two factors.

❑ 1. Electrostatic Repulsion: Coulombic repulsion energy caused by having two

electrons in same orbital. Destabilizing energy contribution of Pc for each doubly
occupied orbital.

❑ 2. Loss of exchange energy; parallel spin() are forced to become antiparallel

(): exchange energy is the driving force of Hund’s rule of maximum spin
multiplicity. With pairing of electrons, the number of electron with a particular spin
is decreased. This will lead to the loss of exchange energy. contribution of Pe for
each pair having same spin and same energy.

P = sum of all Pc and Pe interactions

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 High Spin vs. Low Spin Complexes
❑ A complex will be high spin or low spin is determined by the Crystal filed splitting
parameter (Δ) and Pairing Energy (P).

❑ For low spin (P < Δ): the energy cost of placing an electron into an already singly
occupied orbital must be less than the cost of placing the additional electron into
an eg orbital at an energy cost of Δ.
❑ For high spin (P > Δ): the energy required to pair two electrons is greater than
the energy cost of placing an electron in an eg, Δ, high spin splitting occurs.
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 Spin-cross over system
❑ When Do ~ P , interconversion between high spin and low spin states (Spin-
cross over) is possible.
❑ Heat, and light etc. can assist this process.

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Appl Nanosci (2020). https://doi.org/10.1007/s13204-020-01420-z
 Key Observations
❑Low spin if ΔO > P, and high spin if ΔO < P
❑3d complexes are high spin with weak field ligands and low spin with
strong field ligands.
❑High valent 3d complexes (e.g., Co3+ complexes) tend to be low spin.

❑4d and 5d complexes are always low spin (large ΔO).

❑For 3d metals low-spin tetrahedral complexes are not common as
tetrahedral splitting is seldom large enough to result in pairing of the
electrons.
❑High and low spin states occur only for 3d metal complexes with
between 4 and 7 d-electrons. Complexes with 1 to 3 d-electrons can
accommodate all electrons in individual orbitals in the t2g set.

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 Crystal Field Stabilization Energy (CFSE)
❑ CFSE is the additional stability which results from placing a transition metal
ion in the crystal field generated by a set of ligands through the splitting of
the d-orbitals.
CFSE = ΔE = Eligand field − Eisotropic field
❑ In this calculation, additional pairing compare to the pre-splitting condition
should be included.
❑ CSFE will depend on multiple factors including:

✓ Geometry
✓ Number of d-electrons
✓ Spin Pairing Energy
✓ Ligand character

❑ For an octahedral complex, an electron in t2g subset will

contributes −2/5 Δo whereas an electron in the higher energy eg
subset contributes to a destabilization of +3/5 Δo .
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 CFSE: Example
high spin d7 octahedral Eisotropic field = 2P
Eligand field = (5 × −2/5Δo) + (2 × 3/5Δo) + 2P
= −4/5Δo+ 2P

CFSE = (−4/5Δo + 2P) − 2P = −4/5Δo

low spin d7 octahedral

Eisotropic field = 2P

Eligand field = (6 × −2/5Δo) + (1 × 3/5Δo) + 3P

= −9/5Δo+ 3P

CFSE = (−9/5Δo + 3P) − 2P = −9/5Δo + P

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 CFSE: for Octahedral Complexes
High Spin Low Spin
d1 t2g1eg0 -2/5 Δo t2g1eg0 -2/5 Δo
d2 t2g2eg0 -4/5 Δo t2g2eg0 -4/5 Δo
d3 t2g3eg0 -6/5 Δo t2g3eg0 -6/5 Δo
d4 t2g3eg1 -3/5 Δo t2g4eg0 -8/5 Δo + P
d5 t2g3eg2 0 Δo t2g5eg0 -10/5 Δo + 2P
d6 t2g4eg2 -2/5 Δo t2g6eg0 -12/5 Δo+ 2P
d7 t2g5eg2 -4/5 Δo t2g6eg1 -9/5 Δo+ P
d8 t2g6eg2 -6/5 Δo t2g6eg2 -6/5 Δo
d9 t2g6eg3 -3/5 Δo t2g6eg3 -3/5 Δo
d10 t2g6eg4 0 Δo t2g6eg4 0 Δo 24
 CFSE: for Tetrahedral Complexes
Configuration CFSE
d1 e1t20 -0.6 Δt
d2 e2t20 -1.2 Δt

d3 e2t21 -0.8 Δt

d4 e2t22 -0.4 Δt
Δt = 4/9 Δo
d5 e2t23 0.0 Δt

d6 e3t23 -0.6 Δt ❑ Tetrahedral splitting is seldom

large enough to result in pairing
d7 e4t23 -1.2 Δt
of the electrons. As a result,
d8 e4t24 -0.8 Δt low-spin tetrahedral complexes
are not common.
d9 e4t25 -0.4 Δt

d10 e4t26 0.0 Δt

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 Octahedral vs. Tetrahedral
❑ assuming high spin configurations. The units are Δo, and Δtet = 4/9 Δo.
ignore their signs since we're looking for the difference between them.

Octahedral Tetrahedral Difference

d0, d5, d10 0 0 0
d1, d6 0.4 0.27 0.13
d2, d7 0.8 0.53 0.27
d3, d8 1.2 0.36 0.84
d4, d9 0.6 0.18 0.42
The ordering of favorability of octahedral over tetrahedral is:
d3, d8 > d4, d9> d2, d7 > d1, d6 > d0, d5, d10
❑If large or highly charged ligands are present, to avoid ligand-ligand
repulsion they may prefer a lower coordination number (4 instead
of 6) 26
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 Octahedral vs. Tetrahedral
❑ In in most cases, CFSE favors octahedral over tetrahedral geometry, but
the degree of favorability varies with the electronic configuration.
❑ For d1 there's only a small gap between the oct and tet lines, whereas at
d3 and d8 there's a big gap.
❑ However, for d0, d5 high spin and d10, there is no CFSE difference between
octahedral and tetrahedral.

❑ If large or highly charged ligands are

present, to avoid ligand-ligand repulsion
they may prefer a lower coordination
number (4 instead of 6)

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