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?
 The d block:
• The d block consists of three horizontal series in
periods 4, 5 & 6
– 10 elements in each series
– Chemistry is “different” from other elements
– Special electronic configurations important
• Differences within a group in the d block are less sharp
than in s & p block
• Similarities across a period are greater
 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?
• Not all d block elements have incomplete d
sub-shells
– e.g. Zn has e.c. of [Ar]3d104s2, the Zn2+ ion
([Ar] 3d10) is not a typical TM ion
– Similarly Sc forms Sc3+ which has the stable e.c
of Ar. Sc3+ has no 3d electrons
 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 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
 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.

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]
 Teeth of a ligand ( teeth  dent)
• 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.
 oxalate ion ethylenediamine
O O 2-
CH2 CH2
C C H2N NH2
O O * *
* *
 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

Ni2+

The chelate effect or chelation is one of the most important

ligand effects in transition metal coordination chemistry.
 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]

 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
 Coordination Equilibria & Chelate effect
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

What are the implications of the following results?
NiCl2 + 6H2O  [Ni(H2O)6]+2

[Ni(H2O)6]+2 + 6NH3  [Ni(NH3)6]2+ + 6H2O log  = 8.6

[Ni(H2O)6]+2 + 3 NH2CH2CH2NH2 (en) log  = 18.3

[Ni(en)3]2+ + 6H2O

[Ni(NH3)6]2+ + 3 NH2CH2CH2NH2 (en) log  = 9.7

[Ni(en)3]2+ + 6NH3
 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 - TS (H -ve, S 0)
 G for the reaction is negative
 Chelate Formation: Major Factors
[Ni(NH3)6]2+ + 3 NH2CH2CH2NH2 (en)

[Ni(en)3]2+ + 6NH3

 en and NH3 have similar N-donor environment

 but en is bidentate and chelating ligand
 rxn proceeds towards right, G negative
 G = H - TS (H -ve, S ++ve)
 rxn proceeds due to entropy gain
 S ++ve is the major factor behind chelate effect
 Chelate Formation: Entropy Gain

Cd2+ + 4 NH3  [Cd(NH3)4]2+ Cd2+ + 4 MeNH2  [Cd(MeNH2)4]2+

Cd2+ + 2 en  [Cd(en)2]2+

G H S
Ligands log 
kJmol-1 kJmol-1 JK-1mol-1

4 NH3 7.44 -42.5 - 53.2 - 35.5

4 MeNH2 6.52 -37.2 -57.3 - 67.3

2 en 10.62 -60.7 -56.5 +13.8

 Chelate Formation: Entropy Gain

Reaction of ammonia and en with Cu2+

[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

[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

 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

 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.

 Important Chelating Ligands
2,3-dimercapto-1-propanesulfonic
acid sodium (DMPS)

Mn+

DMPS is a effective chelator with two groups thiols - for

mercury, lead, tin, arsenic, silver and cadmium.
 SH O

HO
OH

O SH Zn
(R,S)-2,3-dimercaptosuccinic acid As
D-Penicillamine
Hg
As, Cu, Pb, Hg Au
Pb

SH S
M+
M As
OH Hg
HS OH S Au
Pb
Dimercaprol
 Important Chelating Ligands
O EDTA O

*O C CH2 CH2 C O*
*
N *
CH2 CH2 N
*O C CH2 CH2 C O*

O O
EDTA: another view
Ca2+
Anticoagulant
Important Chelating Ligands

Macrocylic Ligands