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Coordination Chemistry

Coordination chemistry deals with the science concerned


with the interactions of ligands with metal centers.

Coordination compounds include compounds of metal atom or ion and


one or more ligands that formally donate electrons to the metal.
Example
[Co(NH3)6]Cl3

[Cu(NH3)4][PtCl4]

[Pt(NH3)2Cl2]

Metals = usually transition metals (Lewis acid)


Ligands = Molecules/ions capable of donating a pair of electron to metal (Lewis
base)
Coordination Compounds

• Ligands
– classified according to the number of donor atoms


Examples
• monodentate = 1
• polydentate
• bidentate = 2 chelating agents
• Tridentate = 3
• tetradentate = 4
(dent  teeth )
• Pentadentate = 5
• hexadentate = 6

EDTA - hexa dentate


Ligands

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Werner’s coordination theory
Werner’s experiment
CoCl3 + 6NH3 + AgNO3 (excess) 3 AgCl ppt

CoCl3 + 5NH3 + AgNO3 (excess) 2 AgCl ppt

CoCl3 + 4NH3 + AgNO3 (excess) 1 AgCl ppt

CoCl3 + 3NH3 + AgNO3 (excess) Zero AgCl ppt

AgNO3 is used to determine quantitatively the amount of chloride.

Q. Why does a stable salt react with varying number of NH3 to give several new
compounds?
Correct formula:
Q. What are their structures? 1. [Co(NH3)6]3+(Cl )3
2. [Co(NH3)5Cl]2+(Cl )2
3. [Co(NH3)4Cl2] +(Cl )1
4. [Co(NH3)3Cl3]
Werner’s coordination theory

Werner explained the nature of chemical bonding in these


complexes assuming two kinds of valence /bonding (primary
valence and secondary valence) of metal atom or ion.

Primary Valence
The number of charges on the complex ion.
These are non directional.
Ex: [Co(NH3)5Cl]Cl2 Primary valence of Co is +2.

Secondary Valence
The number of ligand atoms coordinated to the metal.
This is also known as coordination number.
These bonds are directional.
Ex: [Co(NH3)5Cl]Cl2 Coordination number of Co is 6. 5
Bonding in coordination compounds

To explain nature of bonding in coordination compounds, several theories developed.

~1930 ~1950 ~1960 ~1980

Valence Crystal field Ligand field theory Angular overlap


bond theory theory or Molecular method
orbital theory

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Crystal Field Theory

It was proposed by Hans Bethe and further developed by Van


Vleck.

CFT-Assumptions
 The interaction between the metal ion and the ligands are purely
electrostatic (ionic).
 The ligands are regarded as point charges or dipoles.
 CFT does not allow ligand electrons to enter metal orbital. Thus
the metal and ligand do not share their electrons.

 Electrons on the metal are under repulsion from those on ligands.


Crystal Field Theory

In order to understand the interaction of crystal or ligand field with valence


orbitals (d-orbitals) of transition metal in complexes, it is necessary to understand
the geometrical relationship of d-orbitals in different geometry of ligands.

along the axis

In between
axis

Pink color = positive sign; white = negative sign 8


Spherical symmetric field

Five d-orbitals of an isolated gaseous transition metal ion are degenerate.

If a spherical symmetric field of negative charges is placed


around the metal, these orbitals remain degenerate (equal
energy), but all of them raised in energy as a result of repulsion
between the negative charge on the ligand and electron(s) in d-
orbital.

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Crystal field effect in octahedral symmetry

Q. How the six d-electrons are filled in the d-orbitals of Co3+ ion in presence of
six NH3 ligands in [Co(NH3)6]3+?

Energy level diagram of d-orbitals in presence of ligands in octahedral geometry

 If we have an electron in each d-orbital, then how much repulsion each


d-orbital feels, by ligands in octahedral geometry (octahedral field),
decide its relative energy.
 If the d-orbital feels more repulsion, then its energy will be higher.
 Since dx2-y2 and dz2 orbitals directed along axial directions and the
ligands come along the axial directions, so these orbitals feel more
repulsion and hence have higher energy.
 dxy, dxz, dyz orbitals directed in between axes and the ligands come
along the axial directions, so these orbitals feel less repulsion and hence
have lower energy.
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Ligands Ligands

z z z

y y y
x x x
dyz dz2 dx2-y2
dz2 dx2-y2
eg

Barycenter
Δo
dxy dxz dyz
t2g
Isolated ion/atom Spherical field Octahedral field
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Crystal field effect in octahedral symmetry
In presence of ligands in octahedral geometry, the d-orbitals split into two
sets, eg and t2g. The energy difference between eg and t2g set of orbitals is
the crystal field splitting energy (Δo).

d-electrons filling in [Co(NH3)6]3+


energy
eg

Δ
3d sub-shell
Co3+ ion
in gas-phase t2g
(d6)
Co(III) in octahedral
complex
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Crystal field effect in square planar symmetry
If one removes the ligands along z-direction, it gives square planar geometry.

In square planar field, the ligands approach the metal ion along x and y-directions.

So the dx2-y2 orbital feels more repulsion energy and hence highest energy.

Orbitals having z-component will experience less repulsions from the ligands and
hence be stabilized.
dx2-y2

dz2 dx2-y2

dxy
Barycenter
dz2

dxy dxz dyz dxz dyz


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octahedral Square planar
Crystal field effect in square planar symmetry

Square planar geometry is favored by metal having d8 electronic configuration in


the presence of a strong field ligand.

Example: [Ni(CN)4]2

Ni+2 (d8 system)


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Crystal field effect in tetrahedral symmetry
 Imagine a tetrahedral molecule inside a cube with metal
ions in the center of the cube. The ligands occupy the
four alternate corners of the cube.

 The two e-orbitals (dz2 and dx2-y2) point


to the center of the face of the cube. The
three t2-orbitals point to the center of
edges of the cube.

 Therefore the t2-orbitals are nearer to


the ligands than e-orbitals.

 Hence t2-orbitals have higher


energy compared to e-orbitals.

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Δt = Δo
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Factors affecting the magnitude of Δ

Number of factors that affect the extent to which d-orbitals split by surround ligands:

1. Oxidation state of the metal ion


The magnitude of Δ increases with increasing oxidation state on the central
metal ion. The nucleus pull the lone pair strongly. The orbital repulsion
Increases.

Complex Δ (cm 1) Oxidation state


[CrF6]2 22,000 +4
[CrF6] 3 15,060 +3
[Ru(H2O)6]3+ 28,600 +3
[Ru(H2O)6]2+ 19,800 +2

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Factors affecting the magnitude of Δ
2. Nature of metal ion
The magnitude of Δ increases from 3d to 4d and to 5d transition elements.

Ex- [Co(NH3)6]3+ Δ = 22,870 cm 1


[Rh(NH3)6]3+ Δ = 34,100 cm 1
The pairing energy decreases as we go from 3d to 4d and to 5d transition
elements. The electro pairing happen easily on metal ion.
Ex- 3d elements P = 15,000-18,000 cm 1
4d, 5d elements P = 8,000-12,000 cm 1

3. Number and geometry of ligands

If there are more number of ligands then there is larger splitting of d-orbitals.
Δt < ΔO Δt = 4/9 ΔO
[VCl4] (Td) Δt = 7,900 cm 1 [VCl6]2 ΔO = 15,400 cm 1
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4. Effect of type of ligand
Different ligands split the d-orbitals of the metal atom/ion to different extent.
Complex Δ (cm 1)
[VCl6]3 ~12,000
[VF6] 3 ~16,000
[V(Urea)6]3+ ~17,000
[V(H2O)6]3+ ~18,000
[V(CN)6]3+ ~23,000

Spectrochemical series:
Organization of ligands according to the magnitude of (Δ) crystal field
splitting energy exerted.
I < Br < SCN < Cl < N3 , F < OH < H2O < NCS < Py, NH3 < en < NO2 < C6H5 < CN < CO

Increasing order of Δ
Weak field ligands: Ligands cause small splitting of d-orbitals.
Strong field ligands: Ligands cause larger splitting of d-orbitals. 19
(kJ/mol) 163 213 259 314

[CrF6]3- [Cr(H2O)6]3+ [Cr(NH3)6]3+ [Cr(CN)6]3-

Spectrochemical series: Increasing D


Qualitative explanation:

I < Br < Cl < F


Smaller the ligand, the closer it comes to the metal ion, thus greater the
repulsion.
F < OH < H2O
F , OH can donate a pair of electrons from their p-orbital to d-orbital of
metal forming a π bond. F , OH are π donor ligands but H2O is not.
This reduces the charge on both ligand and metal resulting less repulsion on
d-orbitals and hence less splitting.
CN < CO
Metal donate electrons to empty atomic orbital or low lying antibonding
MO of ligand, resulting a π bond. PPh3 , CN , CO are π acceptor
ligands.
When a bond forms by donation of electron from metal to ligand, it is
called as back bonding.
Combination of bonding and back bonding creates strong bonding in
complexes containing PPh3 , CN , CO ligands. 21
Crystal Field Stabilization Energy (CFSE)

Occupation of the
lower energy d-orbitals by electrons causes a stabilization of the complex.
higher energy d-orbitals causes a rise in energy of the complex.

In octahedral field

CFSE = [ 0.4 n(t2g) + 0.6 n(eg)] Δo


In tetrahedral field

CFSE = [ 0.6 n(e) + 0.4 n(t2)] Δt

where n(t2g) and n(eg) are the numbers of electrons in the t2g and eg levels
respectively in octahedral complex.

And n(t2) and n(e) are the numbers of electrons in the t2 and e levels
respectively in octahedral complex.

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CFSE in octahedral field
d1-d3
If there are one to three valence electrons present in metal ion, the t2g orbitals are
filled in an octahedral geometry of ligands.

So the CFSE will be 0.4Δo, 0.8Δo and 1.2Δo for d1, d2 and d3 electronic
configuration, respectively.
eg

Barycenter

d4-d7 t2g
Two possibilities.
The electron may enter the higher energy, eg, level.
(High spin complexes, seen in weak field ligands.

Or, it may pair up with another electron in one of the t2g orbital.
Low spin complexes, observed in strong field ligands.
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When the 4th electron is assigned it 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 (Coulombic repulsion energy and exchange
energy)
d4

Strong field = Weak field =


Low spin High spin
(2 unpaired) (4 unpaired)

[Mn(CN)6]3- Do >P Do<P [Mn(H2O)6]3+


Strong field Complex Weak Field Complex
Low Spin Complex High Spin Complex
CFSE in octahedral field
d4-d7
The actual configuration depends on the relative magnitude of Δo and P (pairing
energy).
Pairing energy is the amount of energy needed to pair up d-electron.

For Δo < P, the fourth electron enters one of the eg orbital. High spin complex
For Δo > P, the fourth electron pair up with one in t2g orbital. Low spin complex

Weak field ligand  smaller Δo  High spin complex


strong field ligand  larger Δo  Low spin complex

Since Δt = 4/9 Δo, all the tetrahedral complexes are high spin complexes.

Q. Calculate the CFSE for d5, d6, d7 metal ions in both high spin and
low spin octahedral complex.
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Among [Fe(H2O)6]3+ and [Fe(CN)6]3 , explain which forms
low spin complex.

[Fe(CN)6]3- Δ = 35,000 cm-1 [Fe(H2O)6]3+ Δ = 13,700 cm-1


P = 19,000 cm-1 P = 22,000 cm-1

eg Paramagnetic
5 unpaired e’s eg
Δ >> P paramagnetic Δ<P
one unpaired e

t2g t2g
low-spin d5 ([Fe(CN)6]3-) high-spin d5 ([Fe(H2O)6]3+)

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Calculation of Crystal Field
Stabilization Energy (CFSE):
The CFSE for some complexes is calculated to be:

[Co(NH3)6]3+: [Cr(en)3]3+

energy
eg eg

t2g t2g
Δ = 22,900 cm-1 Δ = 21,900 cm-1

CFSE = 22,900(0.4 x 6 – 0.6 x 0) CFSE = 21,900(0.4 x 3 – 0.6 x 0)

= 54,960 cm-1 = 26,280 cm-1


Strong field
Placing electrons in d orbitals
Weak field
environment environment
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.


u.e. = un paired electrons
High Spin Vs. Low Spin (d1 to d10)

High spin

Only the d4 through d7 cases have both high-spin and low-spin


configurations.
Octahedral, Tetrahedral & Square Planar
•CF Splitting pattern for
various molecular geometry
dx2-y2 dz2
dx2-y2

Octahedral
Tetrahedral dxy dyz dxz dxy
Square planar
M
M M

dz2

dx2-y2 dz2 dxz dyz


dxy dyz dxz
Pairing energy Vs. D Mostly d8
Small D  High Spin
Weak field D < P (Majority Low spin)
Strong field D > P Strong field ligands
i.e., Pd2+, Pt2+, Ir+, Au303+
Chelating Ligands

Ligands with two or more points of attachment to the metal atom/ion are called as
chelating ligands.
The complex compounds containing such type of ligands are called as chelates.

Common multidentate (chelating) ligands

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Examples of Chelating Ligands

Porphyrin

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Stability of Chelates
The chelates are more stable than similar complexes with unidentate ligands
Cu2+ + 2(en) [Cu(en)2]2+ (1)
Cu2+ + 4 MeNH2 [Cu(MeNH2)4]2+ (2)
Equilibrium ΔG ΔH /kJ mol 1 TΔS /kJ mol 1

1 60.67 56.48 4.19


2 37.40 57.30 19.9
Higher stability of chelates is due to
i) More no. of bonds have to be simultaneously broken to detach the ligand
ii) Entropy factor: Entropy is less for higher chelating number.
• More the rings are formed more will be the stability
• Among the ring structures five and six membered rings are
more stable
• For smaller and larger ring sizes the steric factors dominate;
rings are strained
• Alternate single and double bonds gives further stability;
conjugation brings delocalization of electrons
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Application of chelation
(1) Used to remove unwanted metal ions in water.

(2) Selective removal of Hg2+ and Pb2+ from body when poisoned.

(3) Prevent blood clots.

(4) Solubilizing iron in plant fertilizer.

(5) Separation of Lanthanides.

•Biologically important chelates:


Haemoglobin (Fe), Chlorophyll (Mg), Vitamine B12 (Co),
Cytochrome oxidase enzyme (Fe, Cu)

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Metal Carbonyls

In metal carbonyl, CO binds to the metal


through its C-donor. Usually the metals in
metal carbonyl are zero-valent
Example:
[Ni(CO)4], [Fe(CO)5], [Cr(CO)6]

CO is a powerful π-acceptor ligand.

Both bonding and back bonding makes


strong bonding in metal carbonyl
compounds.

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Why in CO, carbon atom participate in bonding with metal

MOT can explain this


In metal carbonyl, the bonding occurs by transfer of electrons from HOMO
of CO to metal atom.
Back bonding occurs by transfer of e- from metal to LUMO of CO.
LUMO

2pz atomic orbital of oxygen has HOMO


contributions to σ*2s, σ2pz and σ*2pz

2pz atomic orbital of carbon has


contributions to σ2pz and σ*2pz

So, the contribution of carbon atom to σ2pz


(HOMO) of CO molecule is large.

The LUMO (π*2px = π*2py) orbitals


have more carbon 2px and 2py character. 36
Metal Carbonyl compounds

Metal carbonyls form one of the oldest (and important) classes of


organometallic complexes. Most metal carbonyls are toxic!
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18 Electron "Rule"
Electron counting is the process of determining the number of valence
electrons about a metal/atom center in a molecule.
Simple compounds from elements in 1st and 2nd period follow octet or 8-electron
(ns2+np6) rule.
Transition metal complexes follow 18-electron (ns2+(n-1)d10 + np6) rule.
the sum of the outer shell electrons possessed by the metal plus those
donated by the ligands (Ex-2 per C≡O) must total eighteen
To determine the electron count for a metal complex:
1. Determine the oxidation state of the transition metal center(s) and count
the number of outer shell electrons.
2. Count the number of electrons being donated to the metal center from
each ligand
3. Add up the electron counts for the metal center and ligands
Complexes with 18 e- counts are referred to as saturated compounds and are more stable.
Complexes with counts lower than 18e- are called unsaturated and can electronically
bind additional ligands.
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Why electron count rule
 Basic tool to understand structure stability
 Predicting reactivity and type of reaction

Basic tool to understand structure stability

Stable compounds.
[Ni(CO)4] [Fe(CO)5] [Cr(CO)6]

Ni(0) = 10 Fe(0) = 8 Cr(0) = 6


4 x CO = 8 5 x CO 10 6 x CO = 12

18 e 18e 18e

Co(Cp)2 Fe(CO)4
Co 9 Fe 8
2Cp 10 4CO 8
Total 19 VEC Total 16VEC
Strong reducing agent. Very reactive (unstable compound)
VEC = valence electrons
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More examples

[V(CO)6] [Mn(CO)6]+ [Fe(CO)4]2-


V(0) = 5 Mn(0) = 7 Fe(0) = 8
6 CO = 12e 6 CO = 12e 4 CO = 8e
1- = +1e 1+ = -1e 2- = 2e

= 18e = 18 e = 18e
Formal oxidation Formal oxidation Formal oxidation
state = V(-1) state = Mn(1) state = Fe(-2)

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Predicting reactivity and type of reaction

Pd(C2H4)Cl2 (14 VEC)

Pd(C2H4)2Cl2
(16 VEC)
Pd(C2H4)2(CO)Cl2 (18 VEC)

Associative reaction favors.

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