Coordination Chemistry

CYN-002

Dr. M. Sankar
D
Department
t t off Ch
Chemistry
i t
 3
Suggested Reference Books
S. Name of the Authors/ Books/Publisher Year of
No Publication
1 J. D. Lee, “Concise Inorganic Chemistry”, 5thh Edition, 1996
Blackwell Science Ltd Reprint:2003
2 J. E. Huheey, E. A. Keiter and R. L. Keiter, “Inorganic 2001
Chemistry: Principle of Structure and Reactivity”, 4th Ed.,
Pearson Education
3 B. H. Madhan, “University Chemistry”, 3rd Edition, 1997
Narosa Publishing
P blishing House
Ho se Reprint 2005
Reprint:2005
4 D. F. Shriver and P. W. Atkins, “Inorganic Chemistry”, 3rd 1999
Edition, Oxford University Press
5 F. A. Cotton, G. Wilkinson, C. A. Murillo and M. Bochmann, 1999
“Advanced Inorganic Chemistry” 6th Edition, Reprint:2003
John Wiley & Sons
Lecture 1
Periodic Table of the Elements 5
18
8GGroups
oups
7 Periods

f-block (Inner Transition Elements)

 Coordination Compounds: An Introduction
Double Salts Coordination Compounds
e.g. KCl MgCl2 6H2O (1) e.g. CuSO4 4NH3 H2O (3)
K2SO4 Al2(SO4)3 24H2O (2) Fe(CN)2 4KCN (4)
1: K+, Mg2+ and Cl− Properties in H2O 3: Doesn’t show Properties of Cu2+, SO42−
2: K+, Al3+ and SO42− -do- 4: -do- Fe2+, CN−
L
Losses th
their
i Id
Identity
tit iin solution
l ti R t i their
Retain th i identity
id tit ini solution
l ti
Deviates the Rule of Valence
hence named “Complex”

Werner Theory:
Primary Valencies, Secondary Valencies
Establish the Structures of [Co(NH3)6]Cl3,[Co(NH
[Co(NH3)5Cl]Cl2, [Co(NH3)4Cl2]Cl
Sidgwick Theory of Effective Atomic Numbers (EAN):
Concept of Coordination, Vacant d-orbitals can accommodate e− pair
from Ligands to attain Noble Gas Electronic Configurations
e.g. Cr(CO)6, [Fe(CN)6]4− Anomalies: [Fe(CN)6]3− , [Ni(NH3)6]2+
6
 Valence Bond Theory
7
B i Concepts
Basic C off VBT
VBT:
1. Ligand (L) forms Coordinate Bond to the Metal (M)
2 L mustt h
2. have Lone
L Pair
P i off e−, M mustt have
h vacantt d-orbitals
d bit l
3. Depending on the Metal Atomic Orbitals − Shape and Stability
Oh Inner
Oh: I (d2sp3),
) Outer
O t (sp
( 3d2),
) SSq. Pl
Planar (sp
( 2d),
d) T
Tetrahedral
t h d l (sp
( 3)
Magnetic Criterion of Bond Type
Shapes of s-, p- and d-orbitals
d-orbitals 8

s-orbital

p-orbitals
Shapes of f-orbitals
9
 Concept of geradeandungerade
Sketches of the Angular parts of Wave functions for s, p, d and forbitals

s orbital Pzorbital
gerade Ungerade

dxy orbital Representation fz3 orbital

gerade Of d-orbital dz2 orbital Ungerade
gerade
 Valence Bond Theory 7

Limitations of VBT:
1. Doesn’t Explain about Color of Transition Metal complexes
2. No details about Variation of Magnetic Properties with Temp.
3. No Quantitative info about Thermodynamic or Kinetic Stability
4. Doesn’t Predict Td? or Sq. Planar? and Strong L? Weak L?
 8
Structures of [PtCl4]2- and [NiCl4]2- according to VBT
 9
Crystal Field Theory (CFT)
 10
CFT Assumptions:
11
 Crystal Field Theory (CFT)
10
Orientation of d-Orbitals in Oh Environment

6L approaches Metal d-orbitals

 11
d-orbitals Splitting in Octahedral
Complexes
+

Color of Transition Metal Complexes: d-d

d d Transition

Factors that can affect ∆o

(i) Th Nature
The N t off the
th Ligands
Li d

(ii) Charge of the Metal ions

(iii) Whether the metal is in I, II or III row of transition elements

 Color of Transition Metal Complexes
The Color of [[Ti(H
( 2O)]
)]3+ UV-Vis Absorption
p Spectra
p of [Ti(H
[ ( 2O)]
)]3+

20,300 cm−1

GS ES
d-d Transition
Wavelength (nm)
Reddish Violet
Low Spin and High Situations for Oh Complexes
a. The Paring Energy and CFSE (∆o)
b Spin only Magnetic Moments
b.
Splitting in Tetrahedral Geometry
Examples, CFSE and Magnetic Moments
Factors Affecting the Magnitude of ∆
Spectrochemical Series
Orientation of d-Orbitals in the Tetrahedral Environment

M L
L
L

4L approaches Metal d
d-orbitals
orbitals
 Spectrochemical Series

I−< Br−< S2−< SCN−<Cl−< NO3−< N3−< F−< OH− <EtOH

< C2O42− ≈ H2O< NCS−< CH3CN <py<NH3<bipy<phen<NO2−

< PPh3< CN ≈ CO

Halide donors < O donors < N donors < C donors

 Concept of Paring Energy (P)
P Energy
P: E required
i d to
t make
k a pair
i ( ) off electrons
l t in
i a single
i l orbital
bit l

Weak Field Ligands Strong Field Ligands

∆o ∆o

High Spin Complexes

Low Spin Complexes

If CFS is very large

large, Paring occurs (i
(i.e.
e CFS > P)
If CFS is rather small, no Paring occurs (i.e. P > CFS)
 Paring Energy (P) vs CFSE
Complex Configuration ∆o (cm−1) P (cm−1) Spin-state

[Fe(H2O)6]2+ d6 10 400
10,400 17 600
17,600 High-spin

[Fe(CN)6]2− d6 32,850 17,600 Low spin

[CoF6]3− d7 13,000 21,000 High-spin

[Co(NH3)6]3+ d7 23,000 21,000 Low-spin

If CFS is very large, Paring occurs (i.e. CFS > P)

If CFS is rather small, no Paring occurs (i.e. P > CFS)
CFSE and Electronic Arrangements in Octahedral Complexes
Weak Field Ligands Strong Field Ligands
No. off d
N
electrons t2g eg CFSE (∆o) t2g eg CFSE (∆o)

d1 −0.4 −0.4
d2 −0.8 −0.8
d3 −1.2 −1.2
d4 −0.6 −1.6 + P
d5 0 −2.0 + 2P

d6 −0.4 + P −2.4 + 3P
d7 −0.8 + 2P −0.8 + 3P
d8 −1.2 + 3P −1.2 + 3P
d9 −0.6 + 4P −0.6 + 4P

d10 0 0
Orientation of d-Orbitals in the Tetrahedral Environment

M L
L
L

4L approaches Metal d
d-orbitals
orbitals
 d-orbitals Splitting in Tetrahedral Complexes
dxy, dyz, dzx
t2
+0 4∆t
+0.4∆
al Energy
y

∆t
Barycenter
Spherical Field −0 6∆t
−0.6∆
Orbita

e
dx2−y2, dz2
Free ion Metal ion in
Tetrahedral Field

∆t=(4/9) ∆o
Features of Tetrahedral Geometry Compare to Oh Environ.

(i) There are 4 only Ligands in the Td complex, and hence the ligand
field is roughly 2/3 relative to Oh

(ii) The direction of L approach in Td Complex doesn’t coincide

with the d-orbitals. This reduces the field by a factor 2/3.

Therefore ∆t is roughly 2/3 × 2/3 = 4/9 ∆o

(iii) As a result, all tetrahedral complexes are high spin since the
CFS Smaller
S ll than th theth paring
i Energy
E
(iv) Hence Low spin Configurations rarely observed. Usually, if a
very strong field ligand is present
present, the square planar geometry
favored

Examples: [FeCl4]−, [CoCl4]22−, [ZnCl4]22−, TiCl4, [MnO4]22−, [FeO4]22−

CFSE and Electronic Arrangements in Tetrahedral Complexes
High Spin Situations Comparison to Oh Environ.
No. off d
N
electrons e t2 CFSE (∆t) ∆t=(4/9)∆o Weak Strong
Field Field
d1 −0 6
−0.6 −0 27
−0.27 −0 4
−0.4 −0 4
−0.4
d2 −1.2 −0.53 −0.8 −0.8
d3 −0 8
−0.8 −0 36
−0.36 −1 2
−1.2 −1 2
−1.2
d4 −0.4 −0.18 −0.6 −1.6
d5 0 0 0 −2 0
−2.0

d6 −0.6 −0.27 −0.4 −2.4

d7 −1.2
12 −0.53
0 53 −0.8
08 −0.8
08
d8 −0.8 −0.36 −1.2 −1.2
d9 −0.4
04 −0.18
0 18 −0.6
06 −0.6
06

d10 0 0 0 0
d-orbitals Orientation in Square Planar
Complexes
 d-orbitals Splitting in Sq. Planar Complexes
dx2−yy2 1.23 ∆o
dx2−y2

eg
gy
Orbiital Energ

∆
dz 2

dxy 0.23 ∆o

Barycenter dz2 −0.43 ∆o

Spherical Field dxy
dyz,dzx
t2g
−0.51 ∆o
dyz,dzx
∆sq. planar=1.3
=1 3 ∆o M

L
 Features of Square Planar Geometry Compare to Others

Square planar coordination is rare except for d8 metal ions

ions.
Among the d8 metal ions exhibiting square planar coordination are

Ni(II) Pd(II),
Ni(II), Pd(II) Pt(II),
Pt(II) Rh(I),
Rh(I) Ir(I),
Ir(I) Cu(III),
Cu(III) Ag(III),
Ag(III) and Au(III)

Cu(II) and Ag(II), both d9 ions, are occasionally found in sq. planar coord.

All known square planar complexes of d8 ions are diamagnetic, because

the highest-energy orbital (dx2-y2) is greatly destabilized, and pairing in
the dxy orbital is more favorable than placing an unpaired electron in
the dx2-y2 orbital.

∆sq. Square Planar Complexes

sq planar=1.3 ∆o
are Diamagnetic
 Factors Affecting the magnitude of ∆
(i) Oxidation State of Metal ion
((ii)) Nature of Metal ion
(iii) Number and Geometry of the Ligands
(i ) Nature
(iv) N t off th
the Ligands
Li d
Oxidation State of Metal ion

Complex ∆o (cm−1)
[Ru(H2O)6]2+ 19,800

[Ru(H2O)6]3+ 28,600

The Magnitude of ∆ increases with increasing ionic Charge of M ion

 Specific About Metal ion

Same Charge and Same Ligands , but different metal ions affects ∆
 Nature of Metal ion

∆ increases
i with
ith a group , the
th trend
t d is
i being
b i 3d < 4d < 5d
On progressing Cr to Mo or Co to Rh, increment is 50% in ∆
Likewise Ir to Rh 25% increment in ∆

4d and 5d transition series have much g

greater tendency
y to
be low spin than do complexes of 3d series
The Number and Geometry of the Ligands

∆t=(4/9) ∆o

∆ for an octahedral complex 2 times higher than Tetrahedral complex

∆sq. planar=1.3 ∆o

∆ for an octahedral complex lower than Square Planar complex

 Spectrochemical Series
I−< Br−< S2−< SCN−<Cl−< NO3−< N3−< F−< OH− <EtOH

< C2O42− ≈ H2O< NCS−< CH3CN <py<NH3<bipy<phen<NO2−

< PPh3< CN ≈ CO

Halide donors < O donors < N donors < C donors

Ligands which cause a small splitting are Weak field ligands

(CFSE in the range 7000 - 30000 cm-1) &
those cause a large splitting are Strong field ligands (CFSE
typically > 30000 cm-1)
The Nature of the Ligands