CHEMICAL BOND

INTERACTION OF ATOMS IN ORGANIC COMPOUNDS

Types of chemical bonds
In accordance with accepted modern classification two main types of chemical
bonds are known:
- ionic;
- covalent.
IONIC BOND
Ionic bond is formed between atoms, which differ in electronegativity.
Ionic bond type is characteristic to inorganic compounds.

COVALENT BOND
Covalent bond is formed between atoms that have identical or close
electronegativities.
Covalent bond is the main type of bond in organic molecules.
For the covalent bond formation each atom provides one electron forming
equally shared electron pair, that belongs to both atoms.
Covalent bond is indicated by the line between atoms when it is drawing

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 Depending on the electronegativity of atoms among which the covalent bond is
formed, it may be:
- polar;
- nonpolar.
If atoms have equal electronegativity, the shared electron pair is on the same
distance from the nucleus of each atom. Such bond is called covalent nonpolar bond:

When the bond appears between atoms with different electronegativity values
the shared electron pair will be shifted toward atom with greater electronegativity. Such
bond is called covalent polar bond:

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 Depending on the number of electron pairs, making covalent bond following
bonds are defined:
– single bond: with one electron pair;
– multiple bonds: with two or three electron pairs:

Donor-acceptor bond or coordinate bond – is a kind of a covalent bond,

which differs by the way of formation.
A donor – is an atom, which has lone pair of electrons, an acceptor – is any
atom (including a proton), which is lack of two electrons to fill the octet.
For example, the formation of ammonium ion proceeds under the donor-
acceptor mechanism:

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 Semipolar bond – is the particular case of the donor-acceptor bond:

Unshared electron pair of nitrogen becomes general (is shared between N and
O); as a result of bond formation oxygen (an acceptor) gets negative charge, and
nitrogen (a donor) gets positive charge. Such bond is called halfpolar and is indicated as
follows:

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 HYDROGEN BOND
Hydrogen bond is formed as a result of electrostatic attraction between
hydrogen atoms, holding partial positive charge and unshared electron pair of other
atom:

Hydrogen bond can be:

- intramolecular:

- intermolecular:

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 STRUCTURE OF ATOM
ATOMIC ORBITALS

An electron is localized on the defined atomic orbital in the atom.

Atomic orbital (AO) – is a region of space, where the probability to find an
electron is the highest.
Depending on the the shape of an atomic orbital (trajectory of electron’s
movement) followings types of AO are known: s-, p-, d-, f-atomic orbitals:

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 HYBRIDIZATION OF ATOMIC ORBITALS
Carbon atom in its ground (not excited) state has two unpaired electrons
(1s22s22p2), but it forms four covalent bonds. This can be explained by the ability of
transferring one 2s-electron to the 2p-subshell (1s22s12p3):

1s 2s 2px 2py 2pz 1s 2s 2px 2py 2pz

↑↓ ↑↓ ↑ ↑ ↑↓ ↑ ↑ ↑ ↑

ground state of carbon atom excited state of carbon atom

So, there are four unpaired electrons on the outermost energy level: one – s and
three – p.
Since chemical bonds are formed by the valent electrons, bonds, for example in
methane (CH4), should have been unequal: one C−H bond is formed by the s-electron,
the other three – by p-electrons.
In fact, all bonds in methane are equal.
To explain this fact, the concept of atomic orbitals hybridization is introduced. The
term hybridization means an interaction, an overlap, a mixing. The interaction of one s-
electron cloud with three p-electron clouds leads to the formation of four qualitatively
new hybridized electron clouds or atomic orbitals:
1s-AO + 3p-AO = 4sp3-AO
The resulting hybrid orbital differs from the s- and p-orbitals, representing a
dumbbell, in which one lobe is much smaller than the other one:
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 sp3-Hybridization of the carbon atom (the first valent state)
sp3-Hybridization state – is the result of interaction between one s- and three p-
atomic orbitals:

Four equal orbitals make the angle of 109º28' between each other and
directed in space from the center of regular tetrahedron to its vertices, therefore sp3-
hybridization is called tetrahedral.
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sp3-Hybridization state of the carbon atom is characteristic for alkanes.
 -Bond formation
Overlapping of sp3-orbitals with other orbitals along the line connecting centers
of atoms results in simple covalent or -bond (Greek “sigma”) formation:

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 sp2-Hybridization of the carbon atom (the second valent state)
sp2-Hybridization state – is the result of interaction between one s- and two p-
atomic orbitals:

Three equivalent sp2-hybrid orbitals are located in one plane under the angle
of 120o, therefore sp2-hybridization is called trigonal.
Unhybridized pz-orbital is situated in a plane which is perpendicular to the plane
of sp2-hybridized orbitals. 10
Such hybridization is characteristic for compounds containing double bonds.
 Bond formation
Due to overlapping of hybridized AOs atoms form -bonds.
Overlapping of two unhybridized p-orbitals in the plane which is perpendicular
to the plane of -bond (overlapping) results in bond formation:

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 sp-Hybridization of the carbon atom (the third valent state)
sp-Hybridization state – is the result of interaction of one s- and one p-atomic
orbitals:

sp-Hybridization is called linear because two hybrid orbitals are located under
the angle of 180o.
Two unhybridized py- and pz-orbitals are in two self-perpendicular planes and
are square to sp-hybrid AOs.
Such type of hybridization is characteristic for compounds with triple bond.12
 sp-Hybridized AOs form -bonds; unhybridized p-orbitals form two bonds
which are in square planes to each other:

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 INTERACTION OF ATOMS IN ORGANIC COMPOUNDS

According to modern conceptions, the reactivity of organic compounds is

defined by the character of electronic density sharing in a molecule and polarizability of
covalent bonds.
An electron shifting in organic compounds is subdivide into two types:
- inductive effect: the shifting of electron density on a chain of -bonds;
- mesomeric effect: – the shifting on a -bond system.

Inductive effect
Between atoms with identical electronegativities the electron pair of the bond
belongs to both atoms in an equal extent (a covalent nonpolar bond); the electron
density in them is shared symmetrically and the molecule has no dipole moment:

If in butane molecule one hydrogen atom is substituted with halogen – chlorine

the electron density of covalent bond С–Сl is shifted to more electronegative chlorine
atom (a covalent polar bond). As a result, not only C-Cl bon is polarized but neighboring
C-C bonds also:
Partial positive charge on carbon
atoms in a chain from С1 to С4 14
decreases: ''''''
 Inductive (induction) effect – is transferring of electron influence of the
substituent through a chain of bonds, which appears due to difference in
electronegativities of atoms.
The inductive effect is designated by the letter І, and the shifting of electron
density is represented by an arrow along simple bond, which edge specifies shifting
direction.

By a direction of electron effect of the substituents positive +І and negative –І

inductive effects are distinguished.
The negative inductive effect is displayed by substituents, which withdraw
electrons of bond: –NO2, –C≡N, –COOH, –Hal, –OH.
The positive inductive effect is displayed by substituents, which are pushing
away electrons of -bond, more often they are alkyl groups (Alk).

Summarizing the above-stated, the main properties of inductive effect are:

1. The inductive effect is displayed only when atoms with different
electronegativity values are in a molecule.
2. The inductive effect propagates only through -bonds in one direction.
3. The inductive effect quickly decays on a chain. A maximum of its action –
four bonds.

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 Mesomeric effect (conjugation effect)

Conjugated system is the system in which the alternation of simple and

multiple bonds takes place or the system in which near to carbon atom with multiple
bond the atom with one, two electronic or vacant p-AO is situated:

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 In conjugated systems additional overlapping of - and p-AO takes place.
Due to the conjugation there is redistribution (delocalization) of -electron
density and formation of common -electron system:

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 Effect of conjugation or mesomeric effect (M) – process of transferring of
electron influence of the substituent through a conjugated system of -bonds.
The mesomeric effect is designated by the letter M, and the shifting of electron
density is represented by a curved arrow ( ).

The positive (+М) and the negative mesomeric effects (-M) are known.
The positive mesomeric effect (+M) is displayed by atoms or atomic groups
with lone pairs of electrons or negative charges (donors of electrons):

The negative mesomeric effect (-M) is displayed by the substituents, which

withdraw electrons of a conjugated system:

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Examples of mesomeric effect of the substituents:

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 Combined displaying of inductive and mesomeric effects of the substituent
The mesomeric and the inductive effects of one substituent can coincide and
not coincide in a direction:

The mesomeric effect of the substituent usually higher than the inductive.

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 Effect of a hyperconjugation
Effect of the hyperconjugation is an interaction which appears by the
overlapping of electron clouds of -orbitals of С–Н bonds with orbitals of a multiple
bond:

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