Coordination Chemistry
Transition elements: partly filed d or f shells
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Tm complex: Variable valence
Sc +3
Ti +1 +2 +3 +4
V +1 +2 +3 +4 +5
Cr +1 +2 +3 +4 +5 +6 Cu is the only element
Mn +1 +2 +3 +4 +5 +6 +7 which affords CuI
Fe +1 +2 +3 +4 +5 +6 compounds without -
Co +1 +2 +3 +4 +5
acceptor ligands
Ni +1 +2 +3 +4
Cu +1 +2 +3
Zn +2
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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.
For a fascinating review on 'ligand' in chemistry - Polyhedron, 2, 1983, 1-7.
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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]
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• Ligands
– classified according to the number of donor
atoms
– Examples
• monodentate = 1 chelating agents
• bidentate = 2
• tetradentate = 4
• hexadentate = 6
• polydentate = 2 or more donor atoms
monodentate, bidentate, tridentate etc. where the concept of teeth (dent)
is introduced, hence the idea of bite angle etc.
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oxalate ion ethylenediamine
O O 2-
CH2 CH2
C C H2N NH2
O O * *
* *
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O EDTA O
*O C CH2 CH2 C O*
*
N *
CH2 CH2 N
*O C CH2 CH2 C O*
O O
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Macrocylic Ligands
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Coordination Numbers and Geometries:
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Coordination Equilibria & Chelate effect
[Fe(H2O)6]3+ + NCS- [Fe(H2O)5(NCS)]2+ + H2O
Kf = [Fe(H2O)5(NCS)]2+/ [Fe(H2O)6]3+[NCS-]
Equilibrium constant Kf formation constant
M + L ML K1 = [ML]/[M][L]
ML + L ML2 K2 = [ML2]/[ML][L]
ML2 + L ML3 K3 = [ML3]/[ML2][L]
MLn-1 + L MLn Kn = [MLn]/[MLn-1][L]
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Coordination Equilibria and Chelate effect
• K1, K2…. Stepwise formation constant.
• To calculate concentration of the final
product, use overall formation constant n:
• n = [MLn]/[M][L]n
• = K1 x K2 x K3 x …. x Kn
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Kinetic stability
Inert and labile complexes
The term inert and labile are relative
“A good rule of thumb is that those complexes that react
completely within 1 min at 25o should be considered labile and
those that take longer should be considered inert.”
Thermodynamically stable complexes can be labile or inert
[Hg(CN)4]2- Kf= 1042 thermodynamically stable
[Hg(CN)4]2- + 4 14CN- = [Hg(14CN)4]2- + CN-
Very fast reaction Labile 13
O O O OH
H2
H3C C C C CH3 H3C C C C CH3
H
keto enol
-H+
actetylacetone
O- O O O-
H 3C C C C CH3 H3C C C C CH3
H H
N
N
1.10 - penanthroline (phen)
2,2’ - Bipyridine 14
Stepwise formation constant of complexes of M2+ generally increases
steadily from Mn2+ to Cu2+ - Irving-William series
Ba2+<Sr2+<Ca2+<Mg2+<Mn2+<Fe2+<Co2+<Ni2+<Cu2+<Zn2+
Radius Electrostatic effect
0.91>0.83>0.82>0.78>0.69 Å
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Example: [Cd(NH3)4]2+
Cd2+ + NH3 [CdNH3]2+ K1 = 102.65
CdNH3]2+ + NH3 [Cd(NH3)2]2+ K2 = 102.10
[Cd(NH3)2]2++ NH3 [Cd(NH3)3]2+ K3 = 101.44
[Cd(NH3)3]2++ NH3 [Cd(NH3)4]2+ K4 = 100.93
Overall: Cd2+ + 4 NH3 [Cd(NH3)4]2+
β4 = K1 x K2 x K3 x K4 = 10(2.65 + 2.10 + 1.44 + 0.93)
= 107.12 16
What are the implications of the following results?
NiCl2 + 6H2O
[Ni(H2O)6]+2
[Ni(H2O)6]+2 + 6NH3
[Ni(NH3)6]2+ + 6H2O
[Ni(NH3)6]2+ + 3 NH2CH2CH2NH2 (en)
[Ni(en)3]2+ + 6NH3
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Complex Formation: Major Factors
[Ni(H2O)6] + 6NH3
[Ni(NH3)6]2+ + 6H2O
NH3 is a stronger (better) ligand than H2O
O NH3 > O H2O
[Ni(NH3)6]2+ is more stable
G = H - TS (H -ve, S 0)
G for the reaction is negative
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Complex Formation: Chelate Effect
• [Ni(NH3)6]2+ + 3 NH2CH2CH2NH2 (en)
[Ni(en)3]2+ + 6NH3
• en is bidentate ligand
• forms a 5 member ring known as chelate ring
• the complex is known as a chelate
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Complex Formation: Chelate Effect
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Coordination Equilibria & Chelate effect
"The adjective chelate, derived from the great claw or
chela (chely - Greek) of the lobster, is suggested for the
groups which function as two units and fasten to the
central atom so as to produce heterocyclic rings."
J. Chem. Soc., 1920, 117, 1456
The chelate effect or chelation is one of the most important
ligand effects in transition metal coordination chemistry. 21
Complex Formation: Chelate Effect
[Ni(NH3)6]2+ + 3 (en) [Ni(en)3]2+ + 6NH3
• Formation of chelate ring reaction proceeds
in forward direction & the product is stable.
This stability is purely kinetic in nature. This
is known as chelate effect.
• G = H - TS (H -ve, S ++ve)
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Compare the β for [Ni(NH3)6]2+ vs. [Ni(en)3]2+
hexa amine: β6 =109
Tris en: β3 = 1018 (Favored product)
Examine: [Ni(NH3)6]2+ + 3 en 6 NH3 + [Ni(en)3]2+
β3 =109.7
Greater number of amine molecules enhances the
disorder of the product, even though the metal
complex is more ordered. (larger ∆S, more negative
∆G) For this process, ∆H is small, only -12 KJ; ∆G
is -67 KJ, leaving -55 kJ for -T∆S.
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Cd2+ + 4 NH3 [Cd(NH3)4]2+
Reaction of ammonia and en with Cd2+
# of S / JK-
G / kJmol-1 H / kJmol-1 1mol-1 log
ligands
2 NH3 -28.24 -29.79 -5.19 4.95
(1 en) (-33.30) (-29.41) (+13.05) (5.84)
4 NH3 -42.51 -53.14 -35.50 7.44
(2 en) (-60.67) (-56.48) (+13.75) (10.62)
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Reaction of ammonia and en with Cu2+
[Cu(H2O)6]2+ + en = [Cu(en)(H2O)4]2+ + 2 H2O
Log K1 = 10.6 H = -54 kJ/mol S = 23 J/K/mol
[Cu(H2O)6]2+ + 2NH3 = [Cu(NH3)2(H2O)2]2+ + 2 H2O
Log 2 = 7.7 H = -46 kJ/mol S = -8.4 J/K/mol
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Chelating agents:
(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) Solubilize iron in plant fertilizer.
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EDTA
2+
Anticoagulant Ca
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Factors affecting the thermodynamic stability
(a) Charge on the metal
Metal ion log
V2+ 12.7 For the formation of EDTA complex
V3+ 25.9
Fe2+ 14.3
Fe3+ 25.1
(b) Steric effect
K (R=H) >> K (R=Me)
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Chelating agents:
(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) Solubilize iron in plant fertilizer.
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2,3-dimercapto-1-propanesulfonic dimercaprol
acid sodium
iminodiacetic acid
triethylenetetraatnine
dipicolinic acid
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desferrioxamine
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The removal of mercury from the mammalian body is most readily effected by
chelating agents which contain sulfhydryl groups: D-penicillamine (DPA), N-
acetyl-D,L-penicillamine, N-acetyl cysteine, meso-2,3 dimercaptosuccinic acid
(DMSA), and sodium 2,3-dimercaptopropane-l-sulfonate (DMPS),
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The use of chelating agents in enhancing the excretion of
copper has been examined because of its relationship to
therapy for Wilson's disease (hepato- lenticular degeneration),
a hereditary disorder in which the normal excretory
processes for copper (via the bile) are defective and in which
copper is accumulated from the diet in the liver and other
organs, to toxic and ultimately lethal levels
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The usual treatment is D-penicillamine.
In some individuals D-penicillamine produces severe adverse
reactions and for these the usual alternative is triethylenetetramine
dihydrochloride
Patients with absent or ineffective erythropoiesis must have their
anemia corrected by blood transfusions. The iron delivered as
hemoglobin from the transfused red cells is not excreted and ultimately
enters body iron stores. Because the underlying disorder is transfusion-
dependent anemia, phlebotomy is not an available option and chelation
must be used to manage the iron burden.
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Some synthetic iron
chelators. Structures
III, deferiprone;
IV, MECAM;
V, DTPA;
VII, 2,3-DHB;
X, EHPG;
XI,cholylhydroxamic
acid;
XII, HBED;
XIII, PIH
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