CHAPTER 2 RESONANCE AND ACID-BASE CHEMISTRY

Resonance is a way of describing bonding in certain molecules or ions by the combination of

several contributing structures (or forms, also variously known as resonance structures or
canonical structures) into a resonance hybrid (or hybrid structure) in valence bond theory.

Resonance may delocalize this the electron pair that the base might use to form the new bond
with the proton. This delocalization increases the stability of the base. ... Since a weaker base
has a stronger conjugate acid, a compound whose conjugate base enjoys resonance stabilization
will be more acidic.

It usually delocalizes electrons from the atom, thus reducing electron density. This causes the
molecule to have lower basicity. Because resonance does not always reduce basicity.
Sometimes it has no effect on it!

Acidity and basicity are two fundamental terms used in chemistry. Acidity is caused by acidic
compounds. Basicity is caused by basic compounds. The key difference between acidity and
basicity is that acidity cause a low pH whereas basicity cause a high pH in an aqueous medium.

In general, the strength of an acid in an organic compound is directly proportional to the

stability of the acid's conjugate base. In other words, an acid that has a more stable conjugate
base will be more acidic than an acid that has a less stable conjugate base.

2.1 COUNTING ELECTRONS

There are two widely used methods for electron counting of complexes - covalent method and
ionic ligand method. Both of the two methods are applicable to all organometallic complexes,
and should give the same electron count.

Covalent Method

In this method, all metal-ligand bonds are considered covalent. Ligands are considered neutral
in charge, and may donate either 2, 1 or zero electrons to the bond. For example, ligands such
as CO and NH3 are considered to have filled valence and contribute 2 electrons. Halide and
hydroxo groups, however, do not have octet structure in neutral state, and contribute 1 electron
to the bonding. Ligands such as BF3 do not have any free electron available, and the two
electrons for bonding would come from the metal center.

Steps for covalent counting method:

1. Identify the group number of the metal center.

2. Identify the number of electrons contributed by the ligands. 3. Identify the overall charge of
the metal-ligand complex.

4. At the presence of metal-metal bond, one electron is counted towards

each metal center in a bond.

5. Add up the group number of the metal center and the e- count of the ligands, then take into
consider the overall charge of the complex to obtain the final electron count.

Ionic Method

The ionic method always assigns filled valences to the ligands. For example, H group is now
considered H, as well as other groups such as halide, hydroxyl and methyl groups. These
groups now contribute one more electron than they do in covalent method, and oxidize the
metal center when a bond is formed. Groups with neutral charge in octet structure, such as CO
and NH3, behaves the same as in valence methods.
Steps for ionic counting method: counting method

1. Determine the overall charge of the metal complex. 2. Identify the charges of the ligands,
and the numbers of e-s they donate.

3. Determine the number of valence electrons of the metal center, so that the oxidation state of
the metal and charges of the ligands balance the overall charge of the complex. (E- count of
metal center = Metal atom group number + (charges of ionic ligands) - overall charge of the
complex)

4. If metal-metal bond is present, one bond counts for one electron for

each metal atom.

5. Add up the electron count of the metal center and the ligands.

2.2 RESONANCE STRUCTURE

A molecule or ion with such delocalized electrons is represented by several contributing

structures (also called resonance structures or canonical forms). A molecule can have
resonance structures when it has a lone pair or a double bond on the atom next to a double
bond.
Rules to remember for recognising resonance structures: Atoms never move. You can only
move electrons in п bonds or lone pairs (that are in p orbitals), the overall charge of the system
must remain the same. The bonding framework of a molecule must remain intact.
A major resonance contributor is one that has the lowest energy. We can often write more than
one Lewis structure for a molecule, differing only in the positions of the electrons. The most
stable structures contribute most to the resonance hybrid. They are called the major resonance
contributors.

The most stable resonance structure will have negative charges on the most electronegative
atoms and positive charge on the least electronegative atoms.

2.3 ORGANIC ACID-BASE

We will look at two definitions for the term's acid and base, the Bronsted Lowry definitions
and the Lewis definitions. We will begin with the Bronsted-Lowry definitions. According to
Bronsted and Lowry, an acid is a species that loses a proton, and a base is a species that gains a
proton. (Remember that positively charged hydrogen ions are called protons.) For example, in
the reaction shown below, hydrogen chloride (HCl) is an acid because it loses a proton, and
water is a base because it gains a proton. The reaction of an acid with a base is called an acid-
base reaction or a proton transfer reaction. Notice that the reverse of an acid-base reaction is
also an acid-base reaction. In the reverse reaction, H3O+ is an acid because it loses a proton,
and Cl- is a base because it gains a proton.
Water can accept a proton because it has two lone pairs, either of which can form a covalent
bond with the proton, and Cl- can accept a proton because any one of its four lone pairs can
form a covalent bond with a proton. Thus, according to the Bronsted-Lowry definitions:

Any species that has a hydrogen can potentially act as an acid. Any species that has a lone pair
can potentially act as a base. Both an acid and a base must be present in an acid-base reaction,
because an acid cannot lose a proton unless a base is present to accept it. Most acid-base
reactions are reversible. Two half-headed arrows are used to designate reversible reactions.

When an acid loses a proton, the resulting species without the proton is called the conjugate
base of the acid. Thus, Cl- is the conjugate base of HCI, and H2O is the conjugate base of
H3O+. When a base gain a proton, the resulting species with the proton is called the conjugate
acid of the base. Thus, HCl is the conjugate acid of Cl-, and H3O+ is the conjugate acid of
H20.

In 1923, G. N. Lewis offered new definitions for the term's acid and base. He defined an acid
as a species that accepts a share in an electron pair and a base as a species that donates a share
in an electron pair. All Bronsted Lowry (proton-donating) acids fit the Lewis definition
because all proton donating acids lose a proton and the proton accepts a share in an electron
pair. (NH3) is a base because it gains a proton, and water is an acid because it loses a proton.
In the reverse reaction, ammonium ion (+NH4) is an acid because it loses a proton, and
hydroxide ion (HO-) is a base because it gains a proton.
Aluminum chloride (AlC13), ferric bromide (FeBr3), and borane (BH3) are acids according to
the Lewis definition because they have unfilled valence orbitals that can accept a share in an
electron pair. These compounds react with a compound that has a lone pair, just as a proton
reacts with a compound that has a lone pair. Thus, the Lewis definition of an acid includes all
proton-donating compounds and some additional compounds that do not have protons.
Throughout this text, the term acid is used to mean a proton-donating acid, and the term Lewis
acid is used to refer to non-proton-donating acids such as AIC13 and BF3. All bases are Lewis
bases because they all have a pair of electrons that they can share, either with a proton or with
an atom such as aluminum, boron, or iron.

SUMMARY

There are two widely used methods for electron counting of complexes - covalent method and
ionic ligand method. For Covalent Method it describe that all metal-ligand bonds are
considered covalent. Ligands are considered neutral in charge, and may donate either 2, 1 or
zero electrons to the bond. And Ionic Method decribes the ionic method always assigns filled
valences to the ligands.

A molecule or ion with such delocalized electrons is represented by several contributing

structures (also called resonance structures or canonical forms). A molecule can have
resonance structures when it has a lone pair or a double bond on the atom next to a double
bond.
According to Bronsted and Lowry, an acid is a species that loses a proton, and a base is a
species that gains a proton. The reaction of an acid with a base is called an acid-base reaction
or a proton transfer reaction. Most acid-base reactions are reversible. Two half-headed arrows
are used to designate reversible reactions. When an acid loses a proton, the resulting species
without the proton is called the conjugate base of the acid.

When a base gain a proton, the resulting species with the proton is called the conjugate acid of
the base. The Lewis definition of an acid includes all proton-donating compounds and some
additional compounds that do not have protons.