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Comparison of Octahedral and Tetrahedral Fields

The document discusses octahedral and tetrahedral crystal fields and factors that influence the magnitude of crystal field splitting (Δ). It explains that [Ti(H2O)6]3+ is a d1 complex that absorbs light at 493 nm, corresponding to a crystal field splitting of 20,300 cm-1. Higher oxidation states, heavier metals, and stronger ligand fields all result in larger Δ values. The spectrochemical series arranges ligands by their ability to split d-orbitals. π-acceptor ligands induce the greatest splitting while π-donors induce the least. High spin and low spin complexes can result depending on whether pairing energy (P) is greater or less than crystal field splitting (Δ

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Shubham Kumar
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2K views

Comparison of Octahedral and Tetrahedral Fields

The document discusses octahedral and tetrahedral crystal fields and factors that influence the magnitude of crystal field splitting (Δ). It explains that [Ti(H2O)6]3+ is a d1 complex that absorbs light at 493 nm, corresponding to a crystal field splitting of 20,300 cm-1. Higher oxidation states, heavier metals, and stronger ligand fields all result in larger Δ values. The spectrochemical series arranges ligands by their ability to split d-orbitals. π-acceptor ligands induce the greatest splitting while π-donors induce the least. High spin and low spin complexes can result depending on whether pairing energy (P) is greater or less than crystal field splitting (Δ

Uploaded by

Shubham Kumar
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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Comparison of Octahedral and Tetrahedral Fields

Determination of Δ

[Ti(H2O)6]3+
Determination of Δ

 [Ti(H2O)6]3+ is a d1 complex. The single electron in the t2g orbitals absorb energy in
the form of light and gets promoted to the eg orbitals to show it’s purple color.

 For [Ti(H2O)6]3+, this corresponds to 493 nm (Δo = 20,300 cm-1 = 243 kJ/mol).

 For t2g1eg0 configuration:


stabilization energy = 243 x 0.4 = 97 kJ/mol,
this extra stabilization due to the splitting of d-orbitals called
crystal field stabilization energy (CFSE).
Factors Influencing the Magnitude of Δ
Δ is Relatable to Colour
 Complementary colour wheel.

Absorb Orange See Blue


Absorb Red See Green
Factors Influencing the Magnitude of Δ
1. Higher oxidation states of the metal atom correspond to larger Δ.

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-

 Higher ionic charge on the metal ion, pulls the ligands closer
towards it and higher electrostatic repulsion results in larger
splitting of d-orbitals
2. In groups, heavier analogues have larger Δ.

For hexaammine complexes


[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.
 For larger metal ion, the ligands experience less steric crowding and
thus approach closer. Thus results in stronger interaction and larger
crystal field splitting.
Factors Influencing the Magnitude of Δ
3. Coordination number/ Geometry has significant effect on Δ.

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+

4. Nature of the ligands.


Effect of Ligands on the Magnitude of Δ
 Example nickel complexes

 Example chromium complexes


Effect of Ligands on Δ: Spectrochemical Series
 An arrangement of ligands according to their increasing ability to split the
d-orbitals or crystal field splitting parameter (Δ).

 Experimentally determined.

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


H2O NCS- CH3CN NH3 en  bipy phen NO2-
PPh3 CN- CO Strong Field
Analysis of the Spectrochemical Series
 Spectrochemical Series cannot be entirely explained by Crystal Field Theory
(CFT).
Examples: why neutral molecules such as H2O are stronger ligands than halides; why
PPh3 and CO are strong field ligands.

 Orbital interactions need to be invoked to rationalize the order of ligands. Thus,


covalency is incorporated into CFT resulting in the Ligand Field Theory.

 We will not discuss detailed Molecular Orbital treatment but will focus on Ligand
Field Theory as a tool to understand important concepts pertaining to the
bonding in Icoordination
Observation: -
 Br- Cl- F-compounds.
(Ligand Field strength)
 In terms of CFT, the fluoride ion being much smaller, can approach closer
to the metal ion thereby increasing the electronic repulsion leading to higher Δ.
Analysis of the Spectrochemical Series
Observation: F-  OH- O2- H2O (Ligand Field strength)
 To explain the above series, let’s look at the bonding modes between the
ligand and the metal. We will consider simplified diagrams for clarity.
 Initially, the ligands can be viewed as having a hybrid orbital or a p orbital
pointing toward the metal to make σ bonds.
 This is referred to as σ donation from the ligand to the metal.

 Hence, all ligands are “σ donors”.

 However, some ligands may have


additional orbitals that can interact
with other orbitals on the metal.
 Ligand Field Theory provides
insights into these additional
interactions as the reasons for the
different strengths of ligands.
Analysis of the Spectrochemical Series
Observation: F-  OH- O2- H2O (Ligand Field strength)
 Ligands which have filled p orbitals may act as p donors by interacting with
suitable metal orbitals.
Interaction between dxy of metal and py of halide:
Reduces positive charge on metal
Reduces Δ

 Water acts only as a sigma-donor ligand.


Analysis of the Spectrochemical Series
Observation: PPh3, CN-, CO are strong field ligands

 Ligands which have empty p or d orbitals may act as p acceptors by


interacting with suitable metal orbitals.

p -back-bonding of ligand with dxy orbital Increases


positive charge on metal
Increases Δ

dp-pp back donation (back bonding)


Analysis of the Spectrochemical Series
 CO also has available p* orbitals for back bonding.
Analysis of the Spectrochemical Series
 PPh3 has dp orbitals for back bonding.

 Accepts electrons from filled metal d-orbital to empty d-orbital of P in PPh3


(p-back bonding)

 In low oxidation states, the electron density on the metal ion is very high.

 To stabilize low oxidation states, we require ligands, which can


simultaneously bind the metal center and also withdraw electron density
from it.
Summary of Ligand Bonding Modes
1. All ligands are σ donors. In general, ligands that engage solely in σ
bonding are in the middle of the spectrochemical series.
2. Ligands with filled p or d orbitals can also serve as π donors. This
results in a smaller value of ∆o.
3. Ligands with empty p, d or π* orbitals can also serve as π acceptors. This
results in a larger value of ∆o.

I-<Br-<Cl-<F-<H2O<NH3<PPh3<CO
π donor< weak π donor<σ only< π acceptor

Examples of donor and acceptor ligands

Sigma donor Pi donor* Pi acceptor*


H2O RO-, R2N- CO, olefin
NR3 F-, Cl- CN-
RCOO- PR3
These ligands also act as s donors.
Significance of Spectrochemical Series
 Lets try to populate the t2g and eg orbitals for octahedral complexes of
different metals (varying number of d-electrons).
 d1-system: no impact of strong field  d2-system: no impact of strong field
or weak field ligand (t2g3 configuration) or weak field ligand (t2g3 configuration)

 d3-system: no impact of strong field  d4-system: Two choices depending


or weak field ligand (t2g3 configuration) on the ligand
To Pair or Not? Pairing Energy (P) Decides
 The pairing energy, P, depends only on the metal, and is made up of two parts.

1. Coulombic repulsion energy caused by having two electrons in same orbital.


Destabilizing energy contribution of Pc for each doubly occupied orbital.

2. Exchange stabilizing energy for each pair of electrons having the same spin
and same energy. Stabilizing contribution of Pe for each pair having same spin
and same energy.

P = sum of all Pc and Pe interactions


P vs. Do: High Spin and Low Spin Complexes

 When the 4th electron will either go into the higher energy eg orbital at an
energy cost of Do or be paired at an energy cost of P, the pairing energy.
High Spin and Low Spin Complexes: Example
 As ligand Changes, electronic configuration also may change (occupancy of t 2g
and eg orbitals may become different).
High Spin and Low Spin Complexes
 Two different configurations are possible for octahedral complexes of metals
with d4, d5, d6, and d7 configurations.

 For d4, d5, d6, and d7 configurations, the magnitude of Δo determines which
configuration is observed.
Curiosity: What Happens When Do is Close to P
 When Do ~ P , interconversion between high spin and low spin states should
be possible

 Has been observed for Fe(II)-d6 systems. Can be brought about by heat and
light
Recap and Some Important Generalizations
 Oxidation state of the metal ion
Δ increases with increase in ionic charge

 Nature of Metal
3d < 4d < 5d

Really large Δ, normally low spin (As you go down the periodic table, Δ increases)

 Number and geometry of ligands


Δtetrahedral only ~50% of Δoctahedral

 3d metals are generally high spin complexes except with very strong ligands.
CN- forms low spin complexes, especially with M3+ ions.

 4d & 5d metals generally have a larger value of ∆o than for 3d metals. As a


result, complexes are typically low spin.

 For 3d metals, tetrahedral splitting is seldom large enough to result in pairing


of the electrons. As a result, low-spin tetrahedral complexes are not common.
CFSE will Vary for Different Electronic Configurations

CFSE = [-0.4 x n(t2g) + 0.6 x n(eg)] Do

where n(t2g) and n(eg) are number of electrons in the respective levels

 Distribution of electrons and CFSE


Electronic Configurations for Tetrahedral Complexes
 Tetrahedral splitting is seldom large enough to result in pairing of the
electrons. As a result, low-spin tetrahedral complexes are not common.

d-electrons configuration CFSE


d1 e1t20 -0.6 Δt
d2 e2t20 -1.2 Δt
d3 e2t21 -0.8 Δt
d4 e2t22 -0.4 Δt
d5 e2t23 0.0 Δt
d6 e3t23 -0.6 Δt
d7 e4t23 -1.2 Δt
d8 e4t24 -0.8 Δt
d9 e4t25 -0.4 Δt
d10 e4t26 0.0 Δt
Tetrahedral Complexes
 If Δt is smaller than Δo (Δt = 4/9 Δo), why would tetrahedral complexes form?

 But what if we take a particular metal ion and a particular ligand? Can we
predict whether it will form an octahedral or a tetrahedral complex, for
example?

 If we make the assumption that Δt = 4/9 Δo, we can calculate the difference in
stabilization energy between octahedral and tetrahedral geometries by
referencing everything in terms of Δo.

 Example Problem:

Which is the preferred configuration for a d3 metal: tetrahedral or octahedral?


Tetrahedral Complexes
 To answer this, the Crystal Field Stabilization Energy has to be calculated for
a  metal in both configurations. The geometry with the greater stabilization will
be the preferred geometry.

 For a d3 octahedral configuration, the CFSE is 3 x -0.4 Δo = -1.2 Δo

 For a d3 tetrahedral configuration (assuming high spin), the Crystal Field


Stabilization Energy is -0.8 Δt

 Remember that because Δtet is less than half the size of Δo, tetrahedral complexes
are often high spin. We can now put this in terms of Δo (we can make this
comparison because we're considering the same metal ion and the same ligand:
all that's changing is the geometry)

 So for tetrahedral d3, the Crystal Field Stabilization Energy is:


CFSE = -0.8 x 4/9 Δo = -0.355 Δo.

 And the difference in Crystal Field Stabilization Energy between the two
geometries will be: 1.2 - 0.355 = 0.845 Δ .
Tetrahedral Complexes
 If we do a similar calculation for the other configurations, we can construct a
Table of Δo, Δt and the difference between them (we'll ignore their signs since
we're looking for the difference between them).

 Plot these numbers.

 Remember: These are CFSE numbers for


hypothetical molecules in octahedral and
tetrahedral geometry.
Tetrahedral Complexes
 Notice that the Crystal Field Stabilization
Energy almost always favors octahedral over
tetrahedral in most cases, but the degree of
favorability varies with the electronic
configuration.

 In other words, 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.

 The order of favourability of octahedral vs


tetrahedral is:

d3, d8 > d4, d9> d2, d7 > d1, d6 > d0, d5, d10
Tetrahedral Complexes: Summary
 The following factors favour tetrahedral complexes:

 Use large ligands.

 Use of metal ions with d0, d5, d10 configuration.

 Use of weak field ligand with other dx configurations

 Examples:

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