METAL IONS IN SOLUTION

1
Principles
z Metal cations in aqueous solution are complexes
of water, similar to complexes of other ligands.

z Water is both a good Lewis base, coordinating

as a ligand via its oxygen to the metal cation,
and a good Lewis acid,
acid coordinating to anions
via its hydrogen atoms.

z It is
i possible
ibl to
t computet the
th heat
h t off solvation
l ti off
cations and anions in passing from the gaseous
phase to water.
2
Mn+ (g) Æ Mn+ ((aq)
q)

H+ (g) Æ H+ ((aq)
q)

At T=298.16 K
∆Go = - 260.5 kcal/mol
∆So = - 31.3 cal/mol K

3
 Heat of Solvation of Metal Cations in
Aqueous Solution
(∆G & ∆H in kcal mol-1; ∆S in cal mol-1K-1)

Ion - ∆G - ∆H - ∆S Ion - ∆G - ∆H - ∆S
H+ 260.5 269.8 31.3 - - - -
Li+ 123.5 133.5 33.7 Fe2+ 456.4 480.2 79.8
Na+ 98.3 106.1 35.3 Co2+ 479.5 503.3 80.0
K+ 80.8 86.1 17.7 Ni2+ 494.2 518.8 82.4
Rb+ 76.6 81.0 14.8 Cu2+ 498.7 519.7 73.9
Cs+ 71.0 75.2 14.1 Zn2+ 484.6 506.8 74.5
Be2+ 582.3 612.6 101.6 Cd2+ 430.5 449.8 65.2
Mg2+ 455.5 477.6 74.3 Hg2+ 436.3 453.7 58.4
Ca2+ 380.8 398.8 60.8 Al3+ 1103.3 1141.0 126.6
Sr2+ 345 9
345.9 363 5
363.5 59 2
59.2 Cr3+ 1037 0 1099.9
1037.0 1099 9 143.9
143 9
Ba2+
05/08/07
315.1 329.5 48.5 Fe3+ 1035.5 1073.4 127.54
Heat of Solvation of Anions in
Aqueous Solution
(∆G & ∆H in kcal mol-1; ∆S in cal mol-1K-1)

Ion - ∆G - ∆H - ∆S
F- 103.8 113.3 31.8
Cl- 75.8 81.3 18.2
Br- 72.5 77.9 14.5
I- 61.4 64.1 9.0
S2- 303.6 309.8 20.5
OH- 90.6 101.2 35.6

5
 H H
O
H H OUTER
O COORDINATION
H

H
H
SPHERE
O

M2+
O

O
O
H

O
H

H
H H H
O
H H

INNER
COORDINATION
SPHERE

M2+
2 ions in water
6
 H H
O
H H
O O
H

H
O

M2+ O S=O
O

O
H

O
H

H H H O
O
H H

Outer - sphere complex of

M2+ ions and SO42- in water

7
 H H
O
H H
O
H

H
O

M2+
O
H

O
H

H H
O
H H

Inner - sphere complex of

M2+ ions and SO42- in water

8
HSAB Concept

Hard Acids Hard Bases

Soft Acids Soft Bases

9
HSAB Concept

Hard Metal Ions Hard Ligand

Soft Metal Ions Soft Ligand

10
Li Be B B C
Hard Acid
Na Mg Al Al Si
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn
Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi

Soft Acid

Borderline
11
 Harder
Base

N O F
P S Cl
As Se Br
Sb Te I
Softer
Base

12
IMPORTANT !!
• It is important to develop an intuitive feeling for the ligand
preferences and rates of complex formation of individual metal
ions. The HSAB approach, however, only provides an indication
of the type of ligand for a metal is likely to prefer.

• Kinetically, two possible mechanisms may be found for complex

formation in aqueous medium : SN1 and SN2 mechanisms.
mechanisms In
both mechanisms, the incoming ligand must first form an outer
sphere complex so that it is properly positioned to move into the
inner sphere
sphere.
13
SN1 Mechanism :
The metal ion must lose a water ligand from its coordination
sphere, lowering its coordination number by one, followed by
the formation of a five coordinate intermadiate
intermadiate, to create a
space which is then filled by the incoming ligand

SN2 Mechanism
M h i :
The incoming ligand first moves into the metal ion coordination
sphere,
p , increasing
g the coordination of the metal ion,, followed
by the formation of a seven coordinate intermadiate, and a
water departing ligand is lost.

14
General Trend :
In general, ability to change coordination number from that
usually favored by metal ion is related to how tightly ligands are
bound to the metal ion.
ion

The small Be (II) ion with its strong covalent M

M--L bonds
strongly favors tetrahedral four coordination, being difficult to
form either three or five coordinate complexes, and therefore
typically reacts very slowly with all ligands.
The large Sr (II) ion has very ionic M-
M-L bond,
bond and very variable
coordination number, easily changes its coordination number, so
very rapidly proceed reaction of ligand substitution.

15
General Rules :

1. For metal ions of the same charge, ligand substitution rates

with the same ligand will increase with increasing the metal
ion size. Typical reaction rates increase :

Be (II) < Mg (II) < Ca (II) < Sr (II) < Ba (II)

or
Al (III) < Ga (III) < In (III) < Tl (III)

16
2. For metal ions of about the same size, ligand substitution
rates with the same ligand will increase with decreasing the
metal ion charge. Typical reaction rates increase :

In (III) < Mg (II) < Li (I) ? ? ? ? ?

17
 FACTORS GOVERNING THE FORMATION
OF UNIDENTATE LIGAND COMPLEXES IN
AQUEOUS SOLUTION

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 THE ROLE OF SOLVENT

z Th solvent
The l t in
i complex
l formation
f ti is
i usually
ll water.
t Water
W t
is both a good Lewis base, coordinating as a ligand via its
oxygen to the metal cation, and a good Lewis acid,
g to anions via its hydrogen
coordinating y g atoms.

z When a strong unidentate ligand such as NH3 and CN-

replaces water molecule on a metal ion to form a complex
in aqueous
aq eo s solution,
sol tion several
se e al factors
fa to s contribute
ont ib te to the final
free energy of complex formation.

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 Protonation in the gaseous phase

Recent studies on gas phase protonation equilibria for

saturated amines are contradicted to intuitive ideas
previously
i l derived
d i d from
f studies
t di off protonation
t ti constants
t t in
i
aqueous solution.

Gas phase entalphy (also free energy) of

protonation :
NH3 << NH2CH3 << NH(CH3)2 << N(CH3)3

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 In aqueous solution :

Amines NH3 NH2CH3 NH(CH3)2 N(CH3)3

pK 9.22 10.60 10.60 9.90

∆Go = - RT ln K ∆Go = 2.303 RT pK

Aqueous phase free energy of protonation :

NH3 < N(CH3)3 < NH2CH3 = NH(CH3)2

Gas phase free energy of protonation :

NH3 << NH2CH3 << NH(CH3)2 << N(CH3)3
12/14/2013 21
 The differences in the energetics
g for amine p
protonation
in gas
gas--phase and in water phase could be explained by
two possible reasons :
The 1st reason :
The role of solvent in dispersing charge from cation to the
solvent by hydrogen bonding
bonding.
The charge dispersion of the cation through hydrogen
bonds stabilizes the cation
cation,, and as hydrogen on the
ammonium cation are replaced by methyl groups,
reducing the number of hydrogen bonding sites.

12/14/2013 22
 For this reason,
reason the basicity of trimethylamine in water is
only slightly higher than that of ammonia, in contrast to
the large difference expected from the gaseous phase
b i iti .
basicities.
basicities
This arises from the lower ability of the
trimethylammonium cation to stabilize itself by hydrogen
bonding, having fewer N-
N-H hydrogens than ammonium
cation..
cation

12/14/2013 23
 H H
O

H CH3
H + H H
+
O H N H O CH3 N H O
H H H
H CH3
O
H H

AMMONIUM TRIMETHYL AMMONIUM

CATION CATION

12/14/2013 24
 The 2nd reason :
The lowering in the basicity of trimethylamine caused
byy factor of steric hindrance for solvation
solvation.. The p
proton
on trimethylammonium cation is unsolvated in the gas
phase, causing only a small steric hindrance between
the coordinated proton and the methyl groups.
In the gas phase, the inductive (releasing electron)
effects of the methyl groups are dominant, and the
order of basicity is :
NH3 << NH2CH3 << NH(CH3)2 << N(CH3)3

12/14/2013 25
 CH3 CH3
H
+ +
CH3 N H CH3 N H O
H
CH3 CH3

GAS PHASE AQUEOUS PHASE

• Proton is not hydrated • Proton is hydrated
• Steric hindrance is less • Steric hindrance is more
important important
• Methyl groups inductive • Methyl
y ggroups
p inductive
effects are apparent effects are not apparent
26
 In General :
The addition of methyl or other alkyl groups to nitrogen
donors has little effects on their aqueous phase
basicity,, and exept for special cases, inductive effects
basicity
are not apparent.
In gas phase :
NH3 << NH2CH3 << NH(CH3)2 << N(CH3)3
PH3 << PH2CH3 << PH(CH3)2 << P(CH3)3
H2O << CH3-OH << (CH3)2O
H2S << CH3-SH << (CH3)2S
12/14/2013 27
 Application of the HSAB Concept

Proton is classified as a hard acid in the HSAB concept.

For that reason,, it is reasonable to expect
p that the
proton affinity :

(CH3)2O > (CH3)2S

(CH3)3N > (CH3)3P

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 Experiments show, however :

(CH3)2O < (CH3)2S

(CH3)3N > (CH3)3P

??
12/14/2013 29
 CH3
CH3
O H
S
CH3 O H CH3

Oxygen in (CH3)2O Sulphur in (CH3)2S

is able to form is not able to form
hydrogen bond hydrogen bond

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 CH3 CH3
H
CH3 N H O CH3 P
CH3 CH3

Nitrogen in (CH3)3N is Phosphorous in

able to form hydrogen (CH3)3P is not able to
bond form hydrogen bond
Since hydrogen bonding is less important in stabilizing
the trimethylammonium cation,
cation, in aqueous solution, the
basicityy of trimethylammonium
y cation is similar to that of
trimethylphosphonium cation
12/14/2013 31
 pK
BASES XH3 XH2CH3 XH (CH3)2 X(CH3)3

X=N 9.2 10.6 10.6 9.9

X=P -14 0.0 3.9 8.7

The trimethylphosphonium cation is only

weakly hydrogen bonded to the solvent, even
though the cation carries a positive charge
charge.
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 I gas phase
In h :
(CH3)2S + (CH3)2OH+ Æ (CH3)2SH+ + (CH3)2O
∆H = - 8 kcal/mol
k l/ l
Thermodynamically
In aqueous phase
p ase : favourable
(CH3)2S + (CH3)2OH+-OH2 Æ (CH3)2SH+-OH2 + (CH3)2O

∆H = + 6 kcal/mol
Thermodynamically
H-bond unfavourable

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 pK
LIGAND
RN(CH3)2 R= CH3 R= C2H5 R= iso C3H7 R= t-
t- C4H9
9.9 10.3 10.5 10.7

The extent of solvation of the proton in the

dimethylalkylammonium cation is so diminished by steric
hindrance that the steric hindrance to solvation
produced by the alkyl groups along the series Me, Et, iso
Pr, t-
t-bu is less important than the increased inductive
effects
In tertiary amines proton basicity in water increases as
the alkyl groups are exchanged along the series
12/14/2013 Me<Et<
Me<Et<isoiso--Pr<t-
Pr<t-Bu. 34