METAL IONS IN SOLUTION

Principles

Metal cations in aqueous solution are complexes of water, similar to complexes of other ligands. 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. It is i possible ibl to t compute t the th heat h t of f solvation l ti of f cations and anions in passing from the gaseous phase to water.
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Mn+ (g) Mn+ ( (aq) q)

H+ (g) H+ ( (aq) q) At T=298.16 K Go = - 260.5 kcal/mol So = - 31.3 cal/mol K

Heat of Solvation of Metal Cations in Aqueous Solution

(G & H in kcal mol-1; S in cal mol-1K-1)

Ion H+ Li+ Na+ K+ Rb+ Cs+ Be2+ Mg2+ Ca2+ Sr2+

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- G 260.5 123.5 98.3 80.8 76.6 71.0 582.3 455.5 380.8 345 9 345.9 315.1

- H 269.8 133.5 106.1 86.1 81.0 75.2 612.6 477.6 398.8 363 5 363.5 329.5

- S 31.3 33.7 35.3 17.7 14.8 14.1 101.6 74.3 60.8 59 2 59.2 48.5

Ion Fe2+ Co2+ Ni2+ Cu2+ Zn2+ Cd2+ Hg2+ Al3+ Cr3+ Fe3+

- G 456.4 479.5 494.2 498.7 484.6 430.5 436.3

- H 480.2 503.3 518.8 519.7 506.8 449.8 453.7

- S 79.8 80.0 82.4 73.9 74.5 65.2 58.4

1103.3 1141.0 126.6 1037 0 1099.9 1037.0 1099 9 143.9 143 9 1035.5 1073.4 127.5 4

Ba2+

Heat of Solvation of Anions in Aqueous Solution

(G & H in kcal mol-1; S in cal mol-1K-1)

Ion FClBrIS2OH-

- G 103.8 75.8 72.5 61.4 303.6 90.6

- H 113.3 81.3 77.9 64.1 309.8 101.2

- S 31.8 18.2 14.5 9.0 20.5 35.6

H O H H H O M2+ O O O

H H H O H O
OUTER COORDINATION SPHERE

2 ions in water M2+

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H H
INNER COORDINATION SPHERE

O H

H O H H H O M2+ O O O

H H H

O S=O O

O
H

H H

Outer - sphere complex of M2+ ions and SO42- in water

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H H O

H O H H O H O M2+ O O

H H

H H

Inner - sphere complex of M2+ ions and SO42- in water

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H H O

HSAB Concept

Hard Acids

Hard Bases

Soft Acids

Soft Bases

HSAB Concept

Hard Metal Ions

Hard Ligand

Soft Metal Ions

Soft Ligand

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Li

Be

B Al Ti V

Hard Acid

B Al

C Si

Na Mg K

Ca Sc Y

Cr Mn Fe Co Ni Cu Zn Ga Ge In Tl Sn Pb Bi

Rb Sr

Zr Nb Mo Tc Ru Rh Pd Ag Cd Hf Ta W Re Os Ir Pt Au Hg

Cs Ba Lu

Soft Acid

Borderline
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Harder Base

N P As Sb
Softer Base

O S Se Te

F Cl Br I

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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.
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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.

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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 MM-L bond, bond and very variable coordination number, easily changes its coordination number, so very rapidly proceed reaction of ligand substitution.

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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)

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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) ? ? ? ? ?

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FACTORS GOVERNING THE FORMATION OF UNIDENTATE LIGAND COMPLEXES IN AQUEOUS SOLUTION

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THE ROLE OF SOLVENT

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 y g atoms. coordinating When a strong unidentate ligand such as NH3 and CNreplaces 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 of f 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 pK
Go = - RT ln K

NH3 9.22

NH2CH3 10.60

NH(CH3)2 10.60

N(CH3)3 9.90

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
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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.
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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 NN-H hydrogens than ammonium cation. cation .

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H H

H O H N H O H O H H +

AMMONIUM CATION
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H O H CH3 H CH3 + N H O H H CH3 TRIMETHYL AMMONIUM CATION

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The 2nd reason : The lowering in the basicity of trimethylamine caused by y 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
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CH3 CH3 N H CH3 GAS PHASE Proton is not hydrated Steric hindrance is less important Methyl groups inductive effects are apparent +

CH3 + CH3 N H O CH3

H H

AQUEOUS PHASE Proton is hydrated Steric hindrance is more important y g groups p inductive Methyl effects are not apparent
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In General : The addition of methyl or other alkyl groups to nitrogen donors has little effects on their aqueous phase basicity, basicity , and exept for special cases, inductive effects 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
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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

??
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CH3 O H CH3 O H

CH3 S CH3

Oxygen in (CH3)2O is able to form hydrogen bond

Sulphur in (CH3)2S is not able to form hydrogen bond

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CH3 CH3 N H CH3 O

H CH3

CH3 P CH3 Phosphorous in (CH3)3P is not able to form hydrogen bond

Nitrogen in (CH3)3N is able to form hydrogen bond

Since hydrogen bonding is less important in stabilizing the trimethylammonium cation, cation, in aqueous solution, the y of trimethylammonium y cation is similar to that of basicity trimethylphosphonium cation
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BASES X=N X=P

pK
XH3 XH2CH3 XH (CH3)2 X(CH3)3

9.2

10.6

10.6

9.9

-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+ (CH3)2SH+ + (CH3)2O H = - 8 kcal/mol k l/ l

In aqueous phase p ase :

Thermodynamic ally favourable

(CH3)2S + (CH3)2OH+-OH2 (CH3)2SH+-OH2 + (CH3)2O H = + 6 kcal/mol

H-bond
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Thermodynamically unfavourable
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LIGAND
RN(CH3)2

pK R CH3 R= 9.9 R C2H5 R= 10.3 R iso C3H7 R= R= R tt- C4H9 10.5 10.7

The trimethylphosphonium cation is only weakly hydrogen bonded to the solvent, even though the cation carries a positive charge.
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PATTERNS IN THE LEWIS ACID ACID-BASE BEHAVIOR IN AQUEOUS SOLUTION

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The HSAB Behavior

It is a matter of fact that Lewis acids and bases can be assigned as hard, soft, or intermediate in a classification called HSAB clasification. It is generally accepted that soft metal ions prefer to combine with ligands of soft donor atom, and hard metal ions prefer to combine with ligands of hard donor atom. Thermodynamically, formation (stability) constant, K, is the experimental measure of such chemical combination, as it is related to the change in (free) energy involved involved.

- Go = RT ln K
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HSAB Approach to the Ionic and Covalent Character of Chemical Bonds :

HARD - HARD

~ ~

Electrostatic i interactions i Electron sharing interactions

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SOFT - SOFT

SMALL METAL ION

SMALL LIGAND

OH2 H2O M OH2

DA large FH-bond?

DB small

No steric hindrance as the ligand is about the same size as the th displaced di l d water t
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SMALL METAL ION

LARGE LIGAND

OH2 H2O M OH2

IDA large DB large

Steric hindrance of solvation

Serious steric hindrance

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LARGE METAL ION

LARGE LIGAND

OH2 H2O M OH2

IDA small DB large

No steric hindrance of the weakly solvated large metal ion

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EDWARD EQUATION (1954) : M+ + L- M-L K= [M[M -L] [M][L]

log Ko = E + H
A constant : Ko = 55.5 x K E = the oxidation potential of the ligand L H = pKa + 1.74
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DRAGO (1971) : A + B A-B KAB = [A[A -B] [A][B]

log

EE
A

C C +DD
A B A

A constant related to KAB

Tendency for electro electrostatic interaction

Correction for steric hindance Tendency for covalent interaction

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The tendency for ionic binding of Lewis acids as measured by IA = EA/CA Lewis Acid IA= EA/CA
A + Au Ag+ Cu+ Hg2+ Pd2+ CH3Hg+ Tl3+ Cu2+ - 16.00 16 00 - 10.60 - 1.30 + 1.63 + 1.85 + 2.50 + 2.66 +2 2.68 68

EA
- 3.00 3 00 - 1.52 - 0.56 + 1.35 + 1.72 + 1.60 + 2.55 +1 1.25 25

CA
0 190 0.190 0.143 0.430 0.826 0.929 0.640 0.960 0 466 0.466

DA
0.0 00 0.0 2.0 0.0 6.0 0.0 0.0 6.0 60
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Lewis Acid IA= EA/CA

H+ Cd2+ Ni2+ Co3+ Zn2+ Co2+ Fe2+ In3+ + 3.04 3 04 + 3.31 + 3.37 + 3.77 + 4.26 + 4.34 + 5.94 +6 6.30 30

EA
+ 3.07 3 07 + 0.99 + 1.20 + 3.30 + 1.43 + 1.33 + 1.40 + 4.49 4 49

CA
+ 1.009 1 009 + 0.300 + 0.300 + 0.875 + 0.312 + 0.276 + 0.256 + 0.714 0 714

DA
20.0 20 0 0.6 4.5 7.0 4.0 3.0 2.0 0.5 05
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Lewis Acid IA= EA/CA

Bi3+ VO2+ Pb2+ Mn3+ Ga3+ Cr3+ Am3+ Fe3+ + 6.39 6 39 + 6.42 + 6.69 + 7.09 + 7.07 + 7.14 + 7.21 + 7.22 7 22

EA
+ 5.91 5 91 + 3.81 + 2.76 + 1.64 + 5.72 + 5.15 + 4.29 +6 6.07 07

CA
+ 0.926 0 926 + 0.593 + 0.413 + 0.223 + 0.809 + 0.721 + 0.595 +0 0.841 841

DA
0.0 00 3.5 0.0 1.0 1.5 1.5 0.0 1.5 15
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Lewis Acid IA= EA/CA

U4+ Sn2+ Pu4+ UO22+ Be2+ Lu3+ La3+ Mg2+ + 7.80 7 80 + 8.07 + 8.31 + 8.40 + 8.84 + 10.07 + 10.30 + 10 10.46 46

EA
+ 7.55 7 55 + 5.65 + 7.90 + 4.95 + 5.43 + 4.57 + 3.90 +1 1.86 86

CA
+ 0.968 0 968 + 0.700 + 0.950 + 0.589 + 0.614 + 0.454 + 0.379 +0 0.178 178

DA
3.0 30 0.0 1.0 0.0 0.0 1.5 15
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Lewis Acid IA= EA/CA

S 3+ Sc Al3+ Ca2+ Y3+ Th4+ Ba2+ Na+ Li+ + 10.49 10 49 + 10.50 + 10.53 + 10.64 + 10.94 + 12.70 + 14.60 + 22 22.20 20

EA
+ 7.03 7 03 + 6.90 + 0.98 + 4.76 + 8.44 + 0.54 + 0.20 +0 0.57 57

CA
+ 0.671 0 671 + 0.657 + 0.093 + 0.477 + 0.771 + 0.043 + 0.014 + 0.026 0 026

DA
0.0 00 2.0 0.0 0.0 0.0 0.0 0.0 0.0 00
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The tendency for ionic binding of Lewis bases as measured by IB = EB/CB Lewis Base IB = EB/CB
FCH3COOOHN3SCNNH3 C5H5N Cl + 0.0 + 0.0 - 0.064 - 0.082 - 0.088 - 0.102 - 0.100 0 100

EB
+ 1.00 1 00 + 0.00 + 0.00 - 0.067 - 0.76 - 1.08 - 0.74 - 1.04 1 04

CB
+ 0.00 0 00 + 4.76 + 14.00 + 10.40 + 9.30 + 12.34 + 7.00 + 10 10.04 04

DB
0.0 00 0.0 0.0 0.2 0.2 0.0 0.0 0.6 06
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Lewis Base SO32BrS2O32INCSHOCH2CH2)2S (NH2)2C=S CN-

IB = EB/CB
- 0.107 0 107 - 0.108 - 0.119 - 0.122 - 0.128 - 0.135 - 0.135 - 0.148 0 148

EB
- 1.94 1 94 - 1.54 - 3.15 - 2.43 - 1.83 - 1.36 - 2.46 - 4.43 4 43

CB
+ 18.20 18 20 + 14.20 + 26.50 + 20.00 + 14.30 + 10.10 + 18.20 + 30 30.00 00

DB
04 0.4 1.0 1.1 1.7 1.0 0.6 0.6 03 0.3
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DRAGO (1971) : A + B A-B KAB = [A[A -B] [A][B]

log

EE
A

C C +DD
A B A

A constant related to KAB

Tendency for electro electrostatic interaction

Correction for steric hindance Tendency for covalent interaction

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