CHAPTER ONE

BONDING, STRUCTURE AND

REACTIVITY

6/14/2024 By: Fikadu G

 Introduction
 Historically, the term organic chemistry dates to the mid-
1700s, when it was used to mean the chemistry of substances
found in living organisms.
 To many chemists, the simplest explanation for the difference
in behavior between organic and inorganic compounds was
that organic compounds contained a peculiar “vital force” as a
result of their origin in living sources.
 B/C of this vital force, chemists believed, organic compounds
could not be prepared and manipulated in the laboratory as
could inorganic compounds.
 This vitalistic theory received a heavy blow when Michel
Chevreul found that soap, prepared by the reaction of alkali
with animal fat, could be separated into several pure organic
compounds, which he termed fatty acids.

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 Cont.…
 Here is example

 A decade later, the vitalistic theory suffered further when

Friedrich Wöhler discovered that it was possible to convert the
inorganic salt ammonium cyanate into the organic substance
urea, which had previously been found in human urine.

 The weight of evidence was clearly against the vitalistic theory

and it was clear that there was no fundamental difference
between organic and inorganic compounds.

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 Cont.…
 The only distinguishing characteristic of organic compounds
is that all contain the element carbon.
 Organic chemistry, then, is the study of carbon compounds.
 Not all carbon compounds are derived from living organisms.
 Modern chemists have developed a remarkably sophisticated
ability to design and synthesize new organic compounds in
the laboratory.

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 Energy levels and Atomic orbitals
 An atom contains a small, dense nucleus made of neutrons
and positively charged protons.
 Most of the mass of an atom is contained in its nucleus.
 Nucleus is surrounded by an extra nuclear space containing
negatively charged electrons.
 Shells(Energy levels) define the probability of finding an
electron in various regions of space relative to the nucleus.
 The energy of electrons in the shells is quantized.
 Quantization means that only specific values of energy are
possible, rather than a continuum of values.

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 Cont.…
 These shells occur only at quantized energies in which three
important effects balance each other.
* Electrostatic attraction that draws the electrons to the nucleus.
* Electrostatic repulsion between the electrons.
* Wavelike nature of an electron that prefers to be delocalized.
 Shells are identified by the principal quantum numbers
1,2,3,,.
 Each shell can contain up to 2(n2) electrons, where n is the
number of the shell.
 Electrons in the first shell are nearest to the positively
charged nucleus and are held most strongly by it; these
electrons are lowest in energy.

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 Cont.…
 Electrons in higher shells are held less strongly by nucleus,
so, these electrons are higher in energy.
 Shells are divided into subshells designated by the letters s, p,
d, and f.
 An orbital is a region of space that can hold two electrons and
has a specific quantized energy.
 The first shell contains a single orbital called a 1s orbital.
 The second shell contains one s orbital and three p orbitals.

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 Electron Configuration of Atoms
 The electron configuration of an atom is a description of the
orbitals its electrons occupy.
 Electron configuration of an atom follows three rules.
 The Aufbau (“Build-Up”): States that orbitals fill in order of
increasing energy, from lowest to highest.
 The Pauli Exclusion Principle: State that only two electrons
can occupy an orbital and that their spins must be paired.
*Two electrons with opposite spins are said to have paired spins.
 Hund’s rule: States that when there are degenerate orbitals
an electron will occupy an empty orbital before it will pair up
with another electron.

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 Covalent bonding in carbon compounds
 An atom may share electrons with one or more other atoms to
complete its valence shell.
 A chemical bond formed by sharing electrons is called a
covalent bond.
 According to valence bond theory, a covalent bond forms
when two atoms approach each other closely and a singly
occupied orbital on one atom overlaps a singly occupied
orbital on the other atom.
 The electrons are now paired in the overlapping orbitals and
are attracted to the nuclei of both atoms, thus bonding the
atoms together.
 The number of covalent bonds an atom forms depends on how
many additional valence electrons it needs to reach a noble-
gas configuration.

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 The Structure of Methane
 Carbon has four valence electrons (2s2 2p2) and forms four
bonds.
 Because carbon uses two kinds of orbitals for bonding, 2s and
2p, we might expect methane to have two kinds of C-H bonds.
 But, all four C-H bonds in methane are identical and are
spatially oriented toward the corners of a regular tetrahedron.
 These tetrahedrally oriented orbitals are called sp3 hybrid
orbitals.
 Note that the superscript 3 in the name sp3 tells how many of
each type of atomic orbital combine to form the hybrid, not
how many electrons occupy it.

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 Cont.…
 When an s orbital hybridizes with three p orbitals, the
resultant sp3 hybrid orbitals are unsymmetrical about the
nucleus.
 One of the two lobes is larger than the other and can therefore
overlap more effectively with an orbital from another atom to
form a bond.
 As a result, sp3 hybrid orbitals form stronger bonds than do
unhybridized s or p orbitals.

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 The Structure of Ethylene
 Carbon atoms can also form double bonds by sharing two
electron pairs between atoms or triple bonds by sharing three
electron pairs.
 For instance, Ethylene has the structure C2H4 and contains a
carbon–carbon double bond, while acetylene has the structure
C2H2 and contains a carbon–carbon triple bond.
 The 2s orbital combines with only two of the three available
2p orbitals.
 Three sp2 hybrid orbitals result, and one 2p orbital remains
unchanged (unhybridized).
 When two carbons with sp2 hybridization approach each
other, they form a strong s bond by sp2–sp2 head-on overlap.
 At the same time, the unhybridized p orbitals interact by
sideways overlap to form what is called a pi (p) bond.

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 Cont.…
 The combination of an sp2–sp2 s bond and a 2p–2p p bond
results in the sharing of four electrons and the formation of a
carbon–carbon double bond.
 Note: The electrons in the s bond occupy the region centered
between nuclei, while the electrons in the p bond occupy
regions above and below a line drawn between nuclei.
 To complete the structure of ethylene, four hydrogen atoms
form s bonds with the remaining four sp2 orbitals.

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 The Structure of Acetylene
 In addition to forming single and double bonds by sharing
two and four electrons, respectively, carbon also can form a
triple bond by sharing six electrons.
 To account for the triple bond in a molecule such as acetylene,
C2H2 we need a third kind of hybrid orbital, an sp hybrid.
 Instead of combining with two or three p orbitals, a carbon 2s
orbital hybridizes with only a single p orbital.
 Two sp hybrid orbitals result, and two p orbitals remain
unchanged.
 The two sp orbitals are oriented 180° apart on the x-axis, while
the p orbitals are perpendicular on the y-axis and the z-axis.
 When two sp-hybridized carbon atoms approach each other,
sp hybrid orbitals on each carbon overlap head-on to form a
strong sp–sp s bond.

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 Cont.…
 At the same time, the pz orbitals from each carbon form a pz–
pz p bond by sideways overlap, and the py orbitals overlap
similarly to form a py–py p bond.
 The net effect is the sharing of six electrons and formation of
a carbon–carbon triple bond.
 The two remaining sp hybrid orbitals each form a s bond with
hydrogen to complete the acetylene molecule.

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 Factors influencing electron availability and
reactivity
A. Inductive effect
 The normal C–C bond has no polarity as two atoms of same
electronegativity (EN) value are connected to each other.
 Consider a carbon chain in 1-Chloro butane, here due to more
EN of Cl atom, C–Cl bond pair is slightly displaced towards
Cl atom hence creating partial negative (–) charge over Cl
atom and partial positive (+) charge over C1 atom.
 Now since C1 is slightly positive, it will also cause shifting of
C1–C2 bond pair electrons towards itself causing C2 to
acquire small positive charge.
 Slightly positive charge creating an induction of charge in
carbon chain. Such an effect is called inductive effect.

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 Cont.…
 Inductive Effect:
 It can also be defined as polarisation of one bond caused by
polarisation of adjacent bond.
 It causes permanent polarisation in molecule, hence it is a
permanent effect.
 Electrons displacement is due to difference in electronegativity
of the two atoms involved in the covalent bond.
 The electrons never leave their original atomic orbital.
 Its magnitude decreases with distance and it is almost
negligible after 3rd carbon atom.
 The inductive effect is always operative through s bond, does
not involve p bond electron.

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 Cont.…
 Types of Inductive effect:
 -I Effect: Electronegative atoms like nitrogen, halogens,
withdraw the electrons of the carbon chain towards themselves
are known to exert -I Effect.
Positively charged species are -I effect.
Example: -H < -C6H5 < -OCH3 < -OH < -I < -Br < -Cl < -F < -
COOH < -CN < - NO2 < -N+(CH3)3
 +I Effect: The atoms/groups which are more electropositive
push the electrons of the carbon chain away from themselves
are known to exert +I Effect.
Negatively charged species are +I effect.
Example: H- < D- < -CH3 < -CH2R < CHR2 < -CR3 < -COO-

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 Cont.…
B. Resonance effect
 is defined as electrons withdrawal and release associated to a
various substituent by pi-electron delocalization.
 Is also the polarity produced in the molecule by the
interaction of two p-bonds or between a p-bond and lone pair
of electrons present on an adjacent atom.
 This is observed in organic molecules that have double bonds.
 Types of Resonance Effects
Positive resonance effect
Negative resonance effect

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 Cont.…
1. Positive Resonance Effect (+R effect): The transfer of
electrons is away from an atom or substituent group attached to
the conjugated system. Eg. –OH,–OR,–OCOR,–NH2,–NHR,

2. Negative Resonance Effect (- R effect): The transfer of

electrons is towards the atom or substituent group attached from
the conjugated system. Eg. -NO2, C=O, -COOH, -C≡N

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 Cont.…
C. Steric Effect
 Chemical reactions are influenced by atoms and molecules
shape and size and geometry of their bond angles.
 An effect on relative reaction rates caused by the space-filling
properties of those parts of a molecule attached at or near the
reacting site called Steric Effect.
 When the spatial arrangement of atoms or groups at or near a
reacting site of a molecule hinders or retards a reaction called
Steric hindrance .

End
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