BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 21
27 Feb 2019
AY 2018-19, Sem-II
Distortions in Complexes
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Lecture 20- Summary
Topics discussed in last class

 Structure of spinels – Explanation by CFT

Calculations of CFSE
 Spin only magnetic moment

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Example – d5 configuration (Oh)
Weak field Strong field

t2g3eg2 eg eg t2g5eg0

E o E o

t2g t2g

CFSE = 0 CFSE = -2o + 2P

The reasoning for including the pairing energy for the low-spin is
that the excess energy required to pair the electron spins should
be added to obtain the net stabilization
BUT HOW MANY P’s TO BE ADDED??
Number of P’s will correspond to number of pairs

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Tetrahedral complexes

Octahedral CFSE = (-0.4nt2g + 0.6 neg) o

Tetrahedral CFSE = (-0.6ne + 0.4 nt2) t

In octahedral cases, CFSE = 0 for d0, d5(weak) and d10 cases;

In Tetrahedral cases, CFSE =0 for d0, d5 and d10 cases irrespective

strong or weak field ligands

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Crystal structure of spinels
Explanation of Crystal Structure of Spinels using CFT:
Spinels, AB2O4: A(II); B(III); O2-
Structure: Cubic Close Packed
Structure of Anions and
cations occupy the empty sites
(holes/ voids)

No. of Tetrahedral sites: 2N

(N= no. of anions per unit cell)
No. of Octahedral sites: N

In normal Spinel: (A2+[B3+2]O42-)

A(II) occupy the tetrahedral sites
B(III) occupy the octahedral sites
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Crystal structure of spinels
Crystal Structure of Spinels:
In Inverse Spinel: (B3+[A2+B3+]O42-)
A(II) occupy the Octahedral sites
B(III) occupy the Octahedral and Tetrahedral sites

Compare the structures of Mn2+Mn23+O4 and Fe2+Fe23+O4

Mn3+ (d4) Mn2+ (d5) Fe3+ (d5) Fe2+ (d6)

CFSE -0.60 Δo 0 0 -0.40 Δo

(Octahedral weak
field)
CFSE (Tetrahedral -0.18 Δo 0 0 -0.27 Δo
weak field)
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Magnetic property – ‘Spin only’
magnetic moment
“Spin only” magnetic moment can be calculated based on the
number of unpaired electron spins
If a complex has ‘n’ unpaired electrons then total spin quantum
number S, as

And spin only magnetic moment is given as m(spin only) with

unit as Bohr Magneton (BM)

The actual/ effective magnetic moment calculations depends

on many factors (not is syllabus)
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Structural aspects of a complex
Structure of coordination compounds are determined by two factors
1) Valence Shell Electron Pair Repulsions. These have to be
minimized for a stable structure.
2) Repulsions between non-bonding d-electrons of the metal and
the ligand electrons. These have also to be minimized.

1. All the six bond pairs are placed at

similar positions then we get a regular
octahedron (All bond lengths are same)

2. If the d-electrons in the metal are

symmetrically placed w.r.t. an octahedral
field.
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Distortion of Oh complexes
 If all the six distances between the ligand and central metal ion
are the same are said to be regular (i.e., symmetrical) octahedral
complexes
 If the distances are not equal are
said to be distorted octahedral
complexes
(a) Diagonally distorted octahedral
complexes - distortion takes place
along a two-fold axis
(b) Trigonally distorted octahedral
complexes -distortion takes place
along a three-fold axis
(c) Tetragonally distorted octahedral
complexes – distortion takes place
along a four fold axis
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Tetragonal Distortion in Oh Complexes

Cube with an octahedron inside Tetragonal system

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Distortion: tetragonal elongation
Tetragonally distorted complexes may be obtained by any of the
following two ways:
(a) If the two trans ligands lying on the z-axis in an octahedron are
moved away from the central metal cation so that their distance
from the metal cation is slightly greater than it is for the other four
ligands lying in the xy plane, we get a tetragonal structure.

[Cu(NH3)4(H2O)2]2+ has a natural

distortion due to different kinds of
bonding (Cu-N and Cu-O)

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Tetragonal elongation
Consider CrF2 solid
Two different types of bond
lengths
Cr-F 1.98 Å (4 bonds)
Cr-F 2.43 Å (2 bonds)
Why?
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Consider CrCl2 solid
Two different types of bond
lengths
Cr-Cl 2.39 Å (4 bonds)
Cr-Cl 2.89 Å (2 bonds)
Distortion: tetragonal compression
(b) If the two trans ligands located at the z-axis are brought near the
central metal cation so that their distance from the metal cation is
smaller than it is for the other four ligands in the xy plane, we again
get a tetragonal structure.
K2CuF4: the Cu2+ ion has two F- at
1.95 Å and four at 2.08 Å

FeF2: the Fe2+ ion has two F- at 1.99 Å

and four at 3.12 Å

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t2g and eg orbital filling
Symmetrical and asymmetrically filled t2g and eg orbitals
The t2g and eg orbital which are empty (t2g0 and eg0), half-filled (t2g3
and eg2) or completely filled (t2g6 and eg4) are said to be symmetrical
orbitals
t2g0, t2g3, t2g6 symmetrical
t2g orbitals
t2g1, t2g2, t2g4, and t2g5 unsymmetrical

eg0, eg4 symmetrical

eg1, eg3 unsymmetrical
eg orbitals
Symmetrical in HS complex
eg 2
Unsymmetrical in LS complex
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Symmetrical electronic arrangements

Electronic Nature of
t2g eg Examples
configuration ligand field

Strong or
d0 TiO2, [TiF6]2-
weak
Strong or [Cr(oxalate)3]3-,
d3
weak [Cr(H2O)6]3+
d5 Weak [MnF6]4-, [FeF6]3-

d6 Strong [Fe(CN)6]4-, [Co(NH3)6]3+

d8 Weak [NiF6]4-, [Ni(H2O)6]2+
Strong or [Zn(NH3)6]2+,
d10
weak [Zn(H2O)6]2+
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Asymmetrical electronic arrangements
Electronic Nature of
t2g eg Examples
configuration ligand field

d1 HS or LS

d2 HS or LS

d4 Strong field (LS)

d4 Weak field (HS) Cr(II) and Mn(III)

d7 Strong field (LS) Co(II) and Ni(III)

Either strong or
d9 Cu(II)
weak

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Condition for distortion
No distortion condition: t2g and eg have symmetrically filled orbitals

Condition for slight distortion: When d-orbitals of the central metal

ion of an octahedral complex have t2g orbitals as unsymmetrically
filled orbitals, there occurs slight distortion in the complex

Condition for strong distortion: When the eg orbitals which point

directly towards the ligands, are unsymmetrically filled, then these
d-electrons repel some ligands more than others and the octahedral
environment becomes distorted. Degeneracy of eg orbitals is
destroyed (lifted). i.e., eg level contains 1, 3, or 2(only in LS complex)
electrons, strong distortion is observed

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Asymmetrical d-electron distribution
Slight distortions
d7 weak field unsymmetrical but the distortion is minimal

This configuration is asymmetric in t2g but symmetric in eg ;

asymmetric filling in t2g produces only minimal distortion.

This explanation is true for d1, d2, d4 (strong), d5 (strong), d6 (weak)

also.

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Tetragonal elongation
Strong distortions
If dz2 is filled and dx2-y2 is unoccupied (i.e., dz2 is in lower
energy compared to dx2-y2), ligands which are approaching
through z direction will be repelled more;
Bond lengths along +z and –z directions increase.

This leads to tetragonal elongation. Two long bonds

When we say dz2 is filled the dxz and dyz will be lowered
compared to dxy. similarly to a smaller extent

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Tetragonal compression
Strong distortions
If dx2-y2 is filled ligands which are approaching through x, y
direction will be repelled more; Bond lengths along +x, +y and
–x, -y directions increase.
This leads to tetragonal compression.
When we say dx2-y2 filled and dz2 is unoccupied then it means
that dx2-y2 is in lower energy compared to dz2
Similarly as before, dxy will be lowered compared to dxz and
dyz to a smaller extent the

Two short bonds

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z-elongation and z-compression

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Jahn-Teller theorem
In 1937, Jahn-Teller theorem explained why certain six-coordinated
complexes undergo distortion to assume distorted octahedral (i.e.,
tetragonal) geometry.

This theorem states that “any non-linear molecular system

possessing degenerate electronic states will be unstable and will
undergo distortion to form a system of lower symmetry and lower
energy and thus will remove degeneracy”.

NB: Jahn-Teller theorem only predicts the occurrence of a distortion;

it does not predict its nature or its magnitude.

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Splitting of t2g and eg levels
The eg and t2g splitting are similar to octahedral splitting
t2g splitting
Consider the t2g splitting in compression; The dxy orbital is lowered
by (2/3)2 w.r.t. original t2g position and correspondingly the two
orbitals dyz and dxz are both raised by (1/3) 2
NOTE: For symmetric distribution no additional stability arises
eg splitting
Unsymmetrical in eg: Will it be Elongation or Compression?
Which orbital will come down and how much will be the splitting is
not given by the theorem
Generally, electron in dz2 has the repulsion only from two ligands
whereas dx2-y2 electrons have repulsion from 4 ligands. Hence in
many cases dz2 is filled and has lower energy than dx2-y2 orbital.
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Example - 1
Examples: [Ni(H2O)6]2+; [Ni(NH3)6]2+

Are these having regular octahedron structures?

Yes ; d8 No Jahn-Teller distortions
d8 configuration in a strong/weak field is t2g6eg2

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Example - 2
[MnF6]4-

Regular
Octahedron

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Example - 3
Example: [MnF2Cl4]4- Example: [MnF4Cl2]4-

Elongation
along z -axis

Compression
along z -axis

Both are cases of natural distortion

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Example - 4
Jahn-Teller theorem is more important in [Cu(H2O)6]2+ than in
[Cu(NH3)4(H2O)2]2+
Cu(NH3)4(H2O)2]2+ has a natural distortion due to different kinds of
bonding, (Cu-N and Cu-O)

Consider [Cu(H2O)6]2+
Regular Octahedron?
No ; d9 Jahn-Teller distortion even
if it has all 6 ligands as same, H2O
Tetragonal system

Reason?? Look at its configuration

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d9 configuration
d9 octahedral (distorted) systems for Cu2+ (in general)

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d9 configuration
d9 octahedral systems e.g. [Cu(H2O)6]2+

1) Only the splitting in eg has been shown. t2g has negligible splitting.
2) 2 electrons are stabilized and 1 electron is destabilized in this
distortion.
3) Thus Cu2+ is more stable in distorted octahedron than in a regular
octahedron.
4) 2 long bonds is z direction; and 4 short bonds in x,y directions –
Tetragonal elongation observed – dz2 orbital is low-lying
Reason: dz2 has the repulsion only from two ligands whereas dx2-y2
electrons have repulsion from 4 ligands. Hence to minimize repulsive
interaction, dz2 is stabilized showing tetragonal elongation
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Extreme elongation
In an extreme elongation case

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Topics discussed
• Distortion in complexes

• Configurations – symmetrically filled and disymmetrically

filled

• Natural distortion – ligand property

• Tetragonal distortions – metal and/or ligand property

• Jahn Teller theorem

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Announcement
Notice – Extra Class

Tutorial Section : 01 and 08 together

Instructor: Dr. Paritosh Shukla
Date: 01 Feb 2019, Friday
Time: 6 pm
Venue: 1201

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