ACIDS AND BASES

REACTIONS AND PROPERTIES OF

LEWIS ACIDS AND BASES

By : DP
6/10/2019 Course : Senyawa Anorganik
Contents
 The fundamental types  Thermodynamic acidity
of reaction parameters
 Displacement reactions  Solvents as acids and
 Metathesis reactions bases
 Hard and soft acids and  Basic solvents
bases:  Acidic and neutral
 Classification of acids solvents
and bases  Heterogeneous acid-
 Interpretation of base reactions
hardness
 Chemical consequences
of hardness
The fundamental types of reaction
 Complex formation
 Remember
that frontier orbitals
define the chemistry
of a molecule CO is a s-donor and
a p-acceptor

d+ d-
C O

M C O

C O M
 Acids and bases (the Lewis concept)

A base is an electron-pair donor

An acid is an electron-pair acceptor

acid adduct base acid complex base

Lewis acid-base adducts involving metal ions
are called coordination compounds (or complexes)
 Frontier orbitals and acid-base reactions

Remember the NH3 molecule

 Frontier orbitals and acid-base reactions

The protonation of NH3

New LUMO

(non-bonding)

New HOMO
(bonding)

(Td) (C3v)
The fundamental types of reaction
 Displacement reactions

MX + Y  MY + X

 Me2O BF3 + py  Me2O + F3B py

 [Fe(OH2)6]3+(aq) + NCS-(aq) 

[Fe(NCS)(OH2)5]2+(aq) + H2O(l)
The fundamental types of reaction
 Metathesis reactions

AX(aq) + BY(aq)  AY(aq) + BX(s)

Me3Si-I + AgBr  Me3Si-Br + AgI

 Hard and Soft Acids and Bases

 Factors other than acid/base strength determine the

acid/base reactivity.
 Silver halide solubility; AgX (s) H

2O
 Ag  (aq)  X  (aq)
 Ksp’s: AgF=205, AgCl=1.810-10, AgBr=5.2 10-13, AgI = 8.3 10-17
 Solvation: F- is much better solvated.
 Degree of Ag-X interaction also plays a role.

 Hard soft acid base (HSAB) theory can help explain the data
 Hard acids and hard bases are small and nonpolarizable.
 Soft acids and soft bases are large and polarizable.
 Hard/hard and soft/soft interactions are most favorable.
 Polarizable – easily distorted by other charged ions.
 Hard and Soft Acids and Bases.

We have already pointed out that the

affinity that metal ions have for ligands
is controlled by size, charge and
electronegativity. This can be refined
further by noting that for some metal
ions, their chemistry is dominated by size
and charge, while for others it is
dominated by their electronegativity.
These two categories of metal ions have
been termed by Pearson as hard metal
ions and soft metal ions. Their
distribution in the periodic table is as
follows:
Hard and soft acids and bases
Interaction between e- pair
donors n acceptors
 Classification of acids and
bases, R.G. Pearson
 Stabilities
of the complex
formation  Constant Kf
 Constant Kf
 Hard Acid: I- < Br- < Cl- < F-
R3P<<R3N; R2S<<R2O
 Soft Acid: F- < Cl- < Br- < I-
R3N<<R3P; R2O<<R2S
 See: Hq, Sc, Zn

The trends in stability constants for complex

formation with a variety of halide ion bases
 Hard and Soft Acids and Bases.

Figure 1. Table showing distribution of hard, soft, and intermediate Lewis

Acids in the Periodic Table, largely after Pearson.
Hard and Soft Acids and Bases

O S- Dithiooxalate ion
can chelate on two sides.
C

C Fe n Cu
-O S
O S
C
- -
C
-O S S
O
C
prefers …er
C prefers …er cations
O S- cations
 Hard and Soft Acids and Bases

Dithiooxalate ion
can chelate on two sides.

O S - - O S
C C
Fe3+ Cu+
C C

O S - - O S

prefers softer
prefers harder cations
cations
Hard and soft acids and bases
 Interpretation of  Hard acids/bases are
small and nonpolarizable
hardness
 Soft acids/bases are
 Hard acid-base large and polarizable
interactions are
 Hard/Hard and Soft/Soft
electrostatic interactions are the most
 Soft acid-base favorable
interactions are  Polarizable = easily
covalent distorted by other
charged ions
Hard and soft acids and bases
 Interpretation of hardness
 Some contributions
 The rearrangement of the
substituents
 Steric repulsion between
substituents
 Competition with the solvent
Hard and soft acids and bases
 Chemical consequences  Example in
of hardness
Hard-hard and soft-soft
interactions help to
systematize complex
formation, but must be
considered in the light of
other possible influences
on bonding.
geochemistry.
 Goldschmidt
classification: lithophile
(rock-loving) and
chalcophile (ore-loving)
elements.
 Silicate mineral (O),
lithium, magnesium,
titanium, aluminium
 Sulfide: selenide,
telluride, Cd, Pb,
Hard and soft acids and bases
 Silicate mineral (O),
lithium, magnesium,
titanium, aluminium
 Sulfide: selenide,
telluride, Cd, Pb,
 The common ores of
nickel and copper are
sulfides. By contrast,
aluminium is obtained
from the oxide and
calcium from the
carbonate. Explaine
these observation in
terms of hardness.
 Hard and Soft Acids and Bases

Hard Soft
non-polarizable polarizable
Small, large,
high charge density low charge
Electrostatic interaction Covalent interaction
cations H+, Groups I & II, Cu+, Ag+, Hg22+,
Ti4+, Cr3+, Fe3+, Co3+ Hg2+, Pd2+, Pt2+

anions N>>P>As>Sb N<<P>As>Sb

O>>S>Se>Te O<<S<SeTe
F>Cl>Br>I F<Cl<Br<I

6/10/2019
HOMO-LUMO Considerations

 Hard-hard interactions can be viewed as simple

electrostatic interactions with the LUMO far above the
HOMO in energy.
 Little change in orbital energies.
 Soft-soft interactions involved HOMO-LUMO energies
that are much closer in energy.
 Large change in orbital energies.
Many studies indicate that the hard-hard interaction is generally
stronger than the soft-soft interaction.
This is a simplistic interpretation.
 idealized Soft Species idealized Hard Species

E
E

small
HOMO/LUMO gap large HOMO/LUMO gap

FMO-Theory for interaction:

Soft-Soft Hard-Hard

E
E

Acid Base

Acid Base

Significant Energy Only neglectable

gain through energy gain through
HOMO/LUMO orbital interaction.
interaction
 CO2R
Enolate alkylation SN2 vs E2
MeI CO2R
soft O
soft
hard Me
R C-Alkylation
CO2R
soft O SN2
Me CO2R
H
R SiMe3
Me3Si–Cl O Br
EtO
hard O-Alkylation
hard Me
R E2

1,2- vs. 1,4-addition to -unsaturated carbonyl compounds

MeLi OH + 0.29 - 0.48

hard
hard Me
O O
soft
O 1,2-Addition H H

Me2CuLi + 0.01
Me O + 0.62
soft

Charge density LUMO-coefficients

1,4- (Conjugate) Addition

Thermodynamic acidity parameters
 The standard  Drago-Wayland
enthalpies of complex parameters for some
formation are acids and bases.
reproduced by the E  A + B  A-B(g)
and C parameters of
the Drago-Wayland
equation that reflect,
in part, the ionic and  E=electrostatic factor
covalent contributions  C=covalent factor.
to the bond in the
complex.
 Quantitative Measures, Drago and
Weyland
 Includes electrostatic and covalent factors to
account more fully for reactivity of an acid-base
system.
 -H=EAEB+CACB
 H is the enthalpy of reaction, A+BAB
 E is a measure of the capacity for electrostatic interactions.
 C is a measure of the tendency to form covalent bonds.
 I2is the reference acid (CA and EA = 1); N,N-
dimethylacetamide and diethyl sulfide are the
reference bases.
 I2 has very little electrostatic attraction for bases (small EA
value); however, it has a strong tendency to form covalent
bonds (high CA values)
 Table E n C
 Drago and Weyland

 2 I + C6H6  I2C6H6
 Another example
 Drago emphasizes to factors involved in acid-base
strength
 Electrostatic and covalency
 If E and C values have been tabulated, Drago’s method
can predict acid-base strength fairly accurately. If no
data is available, Pearson’s HSAB method can be useful
for rough predictions. Neither method covers every case.
Additionally, neither method includes solvation effects.
Solvents as acids and bases
 Basic solvents  Example:
 Acidic and neutral
solvents
 Basic solvents  O2S-DMSO + NH3 
 Basic solvent are O2S-NH3 + DMSO
common, they may
form complexes with  Silver perchlorate
the solute and particle AgClO4, more soluble
in displacement in benzene than in
reactions. alkane. Account for this
 Water, alcohol, ether, observation.
amines, DMSO
 Acidic and neutral H-O-H NH3 + H3O+
solvents  H-NH3 + 2 H2O
 Hydrogen bond
formation is an Liquid sulfur dioxide (soft
example of Lewis acidic solvent) for soft
complex formation; base benzene
other solvents may
also show Lewis acid
character.
Protic Solvents act as hydrogen bond donors which solvate anions (especially hard
electronegative oxygen). This leaves the soft atom of the nucleophile free to react.
OH

O M O OH

Br

M = Li, Na

DMF 100% 0% DMF, THF, Et2O and toluene

give exclusively O-alkylation.
THF 100% 0%
Protic solvents for example
Toluene 97% 0%
simple aliphatic alcohols do
(MeOH, EtOH,t-BuOH) 100% 0% not have enough H-bonding
capacity to change from O to
H2O 51% 38% C-alkylation.
Phenol 23% 77% However, H2O, phenol and
2, 2, 2-Trifluoroethanol 37% 42% fluorinated alcohols form far
stronger hydrogen bonds 
significant C-alkylation
Heterogeneous acid-base reactions
 Thesurfaces of many
catalytic materials and
minerals have Bronsted
and Lewis acid sites.
 Acidity in zeolites
Acid site inside
10 MR pore

3610cm-1

 Strength of acid sites depends on T-O-T angle

T-O-T angle depends on framework structure, Al-
content, nature of T-ion etc.
In zeolites and silica-alumina Brönsted acid sites
Transform into Lewis acid sites on heating
Bronsted acid sites

H+ H+
O O O O O O O
- -
Si Al Si Si Al Si [A]

- H2O

Basic site Lewis acid site

O O O O O O [B]
- +
Si Al Si Si Al Si
 Technical Barriers Addressed:
Chemicals and Materials
Transesterification:
O
O C R1 OH
O O
MeOH
Oil O C R2
O
OH Glycerol + MeO C R' Biodiesel
Base Catalyst
O C R3 OH R' = R1, R2, R3

Animal Fat or
Restaurant Oil Biodiesel
Base catalyst destroyed
by FFA’s (soap formation)

Fatty acid free Oil

Esterification Transesterification
by acid catalyst by base catalyst
O O
H+
R OH MeOH R OMe
 Technical Barriers Addressed:
Chemicals and Materials
O
H3C O C R Biodiesel
Free Fatty Acid
O
HO C R
Biodiesel
Triglyceride
O O
H2C O C R H3C O C R
O
SO3H
HC O C R1
O O
H2C O C R2 H2C O C R
O O
OH OH OH
HC O C R1 H3C O C R
H2C C CH2
O
H2C O C R2
H = Sulfonic Acid
Si
O O
O
O
H3C O C R OH OH OH
H2C C CH2
H

= Calcium Oxide
H2C OH
Nanoparticle
HC OH

H2C OH
Glycerol

J. A. Nieweg, C. Kern, H.-T. Chen, Y. Huang, and V. S.-Y. Lin* Angew. Chem. Int. Ed. 2005, submitted.
Latihan
1. Gunakan konsep asam-basa untuk
mengomentari fakta bahwa bijih merkuri yg
penting adalah cinnabar, HgS, sedangkan seng
terjadi di alam sebagai sulfida, silikat, karbonat,
dan oksida.
2. Unsur blok f didapati sebagai M(III) litofil dalam
mineral silikat. Apakah hal ini dapat
mengindikasikan hardness?
 Jelaskan trend hardness/softness dalam sistem
periodik

C N O F

P S Cl

As Se Br
I
 Jelaskan bonding antara kompleks
 tiosianatdengan ion logam Fe dan Au.
 sianat dengan ion logam Fe dan Au.