Inorganic Chemistry (CY11003)

1b-Bonding in coordination compounds

Prof. Madhab Chandra Das

Department of Chemistry
High Pressure Lab (Ground Floor)
Ph: 03222-282894
Email: mcdas@chem.iitkgp.ac.in
 Bonding in coordination compounds

• Introduction….
Nobel prize 1913
• Alfred Werner - 1893
• VBT
• Crystal Field Theory (CFT)
• Modified CFT, known as
Ligand Field Theory
• MOT
[Fe(H2O)6]3+ [Ni(H2O)6]2+ [Zn(H2O)6]2+
[Co(H2O)6]2+ [Cu(H2O)6]2+
 Gemstone owe their color from
trace transition-metal ions
• Corundum mineral, Al2O3: Colorless
• Cr  Al : Ruby
• Mn  Al: Amethyst
• Fe  Al: Topaz
• Ti &Co  Al: Sapphire

• Beryl mineral, Be3 Al 2Si6O18: Colorless

• Cr  Al : Emerald
• Fe  Al : Aquamarine
 Coordination Chemistry

Transition elements: partly filed d or f shells

Which elements should be considered as transition elements?

Why do we consider the 1st row separately from others?
 What is a transition metal?
• Transition metals [TM’s] have characteristic
properties
– e.g. coloured compounds, variable oxidation states
• These are due to presence of an inner incomplete d
sub-shell
• Electrons from both inner d sub-shell and outer s
sub-shell can be involved in compound formation
 What is a transition metal?

• For this reason, a transition metal is defined

as being an element which forms at least
one ion with a partially filled sub-shell of d
electrons.
– In period 4 only Ti-Cu are TM’s!
– Note that when d block elements form ions the
s electrons are lost first
 TM complex: Variable valence

Sc +3

Ti +1 +2 +3 +4
V +1 +2 +3 +4 +5
Cr +1 +2 +3 +4 +5 +6
Mn +1 +2 +3 +4 +5 +6 +7
Fe +1 +2 +3 +4 +5 +6

Co +1 +2 +3 +4 +5

Ni +1 +2 +3 +4

Cu +1 +2 +3

Zn +2
 Complexes: Have metal ion (can be zero oxidation state)
bonded to number of ligands.
Complex contains central metal ion bonded to one
or more molecules or anions
Lewis acid = metal = center of coordination

Transition metals can act as Lewis acid

Lewis base = ligand = molecules/ions covalently
bonded to metal in complex

The term ligand (ligare [Latin], to bind) was first used by

Alfred Stock in 1916 in relation to silicon chemistry. The first use
of the term in a British journal was by H. Irving and R.J.P. Williams
in Nature, 1948, 162, 746.
Ligand: Lewis base – contain at least one nonbonding pair of
electrons
Ni2+(aq) + 6NH3(aq)  Ni(NH3)62+(aq)
Lewis acid Lewis base Complex ion

Coordination compound
Compound that contains 1 or more complexes
Example
[Co(NH3)6]Cl3

[Cu(NH3)4][PtCl4]

[Pt(NH3)2Cl2]
 How & Why?

Werner’s theory can’t predict the geometry of the complex

 Valance Bond Theory

Basic Principle

A covalent bond forms when the orbtials of two

atoms overlap and are occupied by a pair of
electrons that have the highest probability of
being located between the nuclei.
Linus Carl Pauling
(1901-1994)
Nobel prizes: 1954, 1962

covalent bond/ coordinate covalent bond

 Valance Bond Model
Ligand = Lewis base
Metal = Lewis acid
s, p and d orbitals give hybrid orbitals with specific geometries
Number and type of M-L hybrid orbitals determines geometry of the complex

Octahedral Complex
e.g. [Cr(NH3)6]3+

CN .....Hybridization.....Shape (All you know already, just to remind you here again)
Tetrahedral e.g. [Zn(OH)4]2- Square Planar e.g. [Ni(CN)4]2-

Limitations of VB theory
Cannot account for colour of complexes
May predict magnetism wrongly
Cannot account for spectrochemical series
400 500 600 800

•The
relationship
between colors
and complex
metal ions
 Crystal Field Model
A purely ionic model for transition metal complexes.
Ligands are considered as point charge.
Predicts the pattern of splitting of d-orbitals.
Used to rationalize spectroscopic and magnetic
properties.
 Octahedral Field

The ligands are approaching along the axes

The orbitals directed along the axes will experience more repulsive force
Thus, dx2-y2 & d z2 will experience stronger repulsion than......
The ligands are approaching along the axes
The orbitals directed along the axes will experience more repulsive force
Thus, d x2-y2 & dz2 will experience stronger repulsion than......
CF Splitting E

d x -y d z2
2 2

+ 0.6 Do
or
+ 6 Dq
Do or 10 Dq

Bary center
- 0.4 Do
or
- 4 Dq

dxy dyz dxz

 Crystal Field Splitting Energy (CFSE)
d1, d2, d3…only one arrangement possible

d4 d5 d6 d7
• In weak/low field (HS): DO  P, => t2g3eg1
• In strong/high field (LS) DO  P, => t2g4
• P: paring energy

How about electronic arrangement d8, d9, d10?

Do it yourself
 What is the crystal field stabilization energy (CFSE) of [Fe(CN)6]3-?
CN- = s.f.l.
C.N. = 6  Oh Fe(III)  d5 h.s. l.s.
CN 3-
eg eg
CN
NC + 0.6 Doct
Fe
NC CN
- 0.4 Doct
CN t2g
t2g

CFSE = 3 x - 0.4 Do
CFSE = 5 x - 0.4 Do + 2P = - 2.0 Do + 2P
+ 2 x 0.6 Do = 0

If the CFSE of [Co(H2O)6]2+ is -0.8 Doct, what spin state is it in?

C.N. = 6  Oh Co(II)  d7 h.s. l.s.

OH2 2+ eg eg
OH2 + 0.6 Doct
H2O
Co
H 2O OH2 - 0.4 Doct
t2g t2g
OH2

CFSE = (5 x - 0.4 Do) CFSE = (6 x - 0.4 Do)

+ (2 x 0.6 Do) = - 0.8 Do + (0.6 Do) + P= - 1.8 Do + P
Atkins: pp476
 In Tetrahedral Field

Approach through alternate corners of cube

Directions x, y, z point to face centers of cube
dx2-y2 & dz2 point along x, y, z directions
Dt = 4/9DO
‘g’ is dropped as no center of symmetry for Td
Square Planar Complexes
Square planar
complexes are quite
common for the d8 metals
in the 4th and 5th periods:
Rh(I), Ir(I), Pt(II), Pd(II)
and Au(III). The lower
transition metals have
large ligand field
stabalization energies,
favoring four-coordinate
complexes.
Square Planar Complexes
The value of ∆sp for a
given metal, ligands and
bond length is
approximately 1.3(∆o).
 Distortion in Octahedral Complex (Jahn-Teller Theorem)
Tetragonal Distortion

[Ni(H2O)6]2+ [Cu(H2O)6]2+
(no J-T distortion) (J-T
distortion)

Symmetrical or
distorted octahedron
Regular octahedron

1937: Hermann Jahn and Edward Teller

In an electronically degenerate state, a nonlinear molecule

undergoes distortion to remove the degeneracy by lowering the
symmetry and thus by lowering the energy.
 What is Electronically Degenerate State?

An electronically degenerate state represents the availability of more than

one degenerate orbitals for an electron. In this condition the degenerate
orbitals are asymmetrically occupied. E.g. the d1 configuration in octahedral
symmetry.

What about d3 configuration?

Symmetrically occupied non-degenerate state NO J-T Distortion

orbitals

Asymmetrically occupied degenerate state J-T Distortion

orbitals
 EXAMPLE

Regular octahedron Regular octahedron

Did we remove degeneracy

after distortion?

Elongation distortion/Z-out Flattening distortion/Z-in

Problem: What if we move to an octahedral complex with a d2 electronic configuration?

…………………………… ……………………………

Elongation distortion/Z-out Flattening distortion/Z-in

we have gained -2/3 δ2 of additional stabilization energy we have gained -1/3 δ2 of additional stabilization energy

 Did we remove degeneracy?

X
31
General Question: Can we tell how big a Jahn-Teller distortion will be?

To an extent

t2g

eg
 Condition of Distortion:

Three
Cases

Slight Distortion Strong Distortion

No Distortion d4, d9 (HS)
d1, d2, d6, d7 (HS)
d0, d 3, d5 d7, d9 (LS)
d1, d2, d4, d5 (LS)
d8, d10 (HS)
d0, d6, d10 (LS)
t2g (unsym) eg (unsym)
t2g (sym) + eg (sym)
33
 Magnitude of D
Oxidation state of the metal ion
[Ru(H2O)6]2+ 19800 cm-1 +2 to +3: 50%
+3 to +4: 30%
[Ru(H2O)6]3+ 28600 cm-1

Number of ligands and geometry

D t< D o Dt= 4/9Do [Co(NH3)4]2+ 5900 cm-1

[Co(NH3)6]2+ 10200 cm-1

Nature of the metal ion

Down the group: IV to V:: 3d to 4d:: area of 4d>3d:: hence higher repulsion
[Co(NH3)6]3+ 23000 cm-1
[Rh(NH3)6]3+ 34000 cm-1
[Ir(NH3)6]3+ 41000 cm-1

Nature of the ligand (weak vs strong field ligand)

Expt detr series by Tsuchida in 1938:
I-<S2-<SCN-<Cl-<NO3-<N3-<F-<OH-<C2O42-<H2O<…..CN-<CO
NH3 is stronger than H2O: couldn’t be explained by CFT
 Uses of CFSE Values
Hydration Enthalpy of M2+ ions (H2O is weak field ligand, the complexes are
high spin).

M2+(g) + 6 H2O(l) = [M(H2O)6]2+(aq) + Hydration Energy

Plotting the enthalpy across the first transition series

CFSE = 0 (Ca/Mn/Zn)
CFSE = -12 Dq (V/Ni)
CFSE = HE calc-HEobs
E required to break the crystals into its constituents
ions or molecules (Born Lande eqn)
Ground-state Electronic Configuration,
Magnetic Properties and Colour
[Mn(H2O)6]3+
Weak Field Complex
the total spin is 4  ½ = 2
High Spin Complex

[Mn(CN)6]3-
Strong field Complex
total spin is 2  ½ = 1
Low Spin Complex
 Placing electrons in d orbitals

d5 d6 d7

1 u.e. 5 u.e. 0 u.e. 4 u.e. 1 u.e. 3 u.e.

d8 d9 d10

2 u.e. 2 u.e. 1 u.e. 1 u.e. 0 u.e. 0 u.e.

 The origin of the color of the transition
metal compounds
E2

DE h

E1

DE = E2 – E1 = h
Ligands influence DO, therefore the colour
The colour can change depending on a number of factors
e.g.
1. Metal charge
2. Ligand strength
The optical absorption spectrum of [Ti(H2O)6]3+

Assigned transition:
t2g eg
This corresponds to
the energy gap
O = 243 kJ mol-1

490 nm
purple
 complementary color chart

observed
color

absorbed
color
• Spectrochemical Series: An order of ligand
field strength based on experiment:
Weak Field I-  Br- S2- SCN- Cl-
NO3- F-  C2O42- H2O NCS-
CH3CN NH3 en  bipy phen
NO2- PPh3 CN- CO Strong Field

H2 N NH2
N
N N N
Ethylenediamine (en)
2,2'-bipyridine (bipy) 1.10 - penanthroline (phen)
Spectrochemical Series
Or more simply :
X<O<N<C
 [CrF6]3- [Cr(H2O)6]3+ [Cr(NH3)6]3+ [Cr(CN)6]3-

As Cr3+ goes from being attached to a weak field

ligand to a strong field ligand, D increases and the
color of the complex changes from green to yellow.
 Colourless?
• For example, although scandium is a
member of the d block, its ion (Sc3+) hasn't
got any d electrons left to move around.

• In the zinc case, the 3d level is completely

full - there aren't any gaps to promote an
electron in to. Zinc complexes are also
colourless.
n = no. of unpaired electrons; spin quantum number S
 = {n(n+2)}1/2 B
 (spin only) = 2{S(S+1)}1/2
Ion n S /B Experimental
Calculate
d
Ti3+ 1 1/2 1.73 1.7 – 1.8
V3+ 2 1 2.83 2.7 – 2.9
Cr3+ 3 3/2 3.87 3.8
Mn3+ 4 2 4.90 4.8 – 4.9
Fe3+ 5 5/2 5.92 5.3

Similar Calculation can be done

for Low-spin Complex
orbital contribution is ignored
Determination Magnetic Properties
Gouy balance to
measure the magnetic
susceptibilities
Limitations of CFT
•Considers Ligand as Point charge/dipole only
•Does not take into account of the overlap of ligand and metal
orbitals and can’t explain partial covalent character of M-L bond
•too much emphasis on metal d orbital but ignore s & p orbitals as
well as ligand pi orbitals
•Can’t explain the relative position of ligand in spectrochemical
series which is expt determined (OH- is weaker than H2O)

Consequence
e.g. Fails to explain why CO is stronger ligand than CN- in
complexes having metal in low oxidation state
Note: You need to know CHELATE EFFECT

•to understand chemistry of transition metal

complexes with multidentate ligands

•to understand mode of action of transition

metal complexes in biology/real life
applications

CHELATE EFFECT will be

discussed in Tutorial Classes