Rigidity of Double /Triple Bonds

H H H H
C sp3 sp3 C C σ bond C
H H H H
H H H H
methyl group methyl group ethane

rotate
FIGURE 1-28
Rotation of single bonds. Ethane
is composed of two methyl groups
bonded by overlap of their sp3 hybrid
orbitals. These methyl groups may
eclipsed staggered rotate with respect to each other.

H H H
C C C C
H H H
FIGURE 1-29
H Rigidity of double bonds. Ethylene is
hold in position try to twist not easily twisted because twisting
overlap destroyed destroys the overlap of its pi bond.

Rotation about single bonds is allowed, but double bonds are rigid and can-
not be twisted under normal conditions.
 Electron Promotion explains Tetravalency of Carbon

an electron in the s orbital is

promoted to the empty p orbital

p p p promotion p p p
s s
carbon’s valence electrons carbon’s valence electrons
before promotion after promotion

Hybridization of Orbitals explains the basis of shapes of Organic molecules

HOW METHANE IS FORMED?

H H
109.5°
H C H C
H H
..

H
H
methane

p p p hybridization
sp3 sp3 sp3 sp3
s
4 hybrid orbitals are formed
4 orbitals are hybridized

when an s and a p ...the s orbital adds to one

orbital overlap... lobe of the p orbital...

◀ Figure 1.5
The s orbital adds to one lobe of
the p orbital and subtracts from the
other. The result is a hybrid orbital
with two lobes that differ in size.

...and subtracts from the

other lobe of the p orbital
to form a hybrid sp3 orbital

the sp3 orbitals are more stable

than the p orbitals and less
stable than the s orbital

hybridization ◀ Figure 1.6

An s orbital and three p orbitals hybridize to
form four sp3 orbitals. An sp3 orbital is more
stable (lower in energy) than a p orbital but
p p p less stable (higher in energy) than an
sp3 sp3 sp3 sp3 s orbital.

s
 ◀ Figure 1.7
For clarity, the smaller lobes of the sp3
a. b. c. orbitals are not shown.
H C H bond formed (a) The four sp3 orbitals are directed toward
by sp3 s overlap
109.5° the corners of a tetrahedron, causing
each bond angle to be 109.5°. This
C arrangement allows the four orbitals to
C be as far apart as possible.
H H (b) An orbital picture of methane, showing
H the overlap of each sp3 orbital of carbon
with the s orbital of a hydrogen.
(c) The tetrahedral bond angle is 109.5°.

The Bonds in Ethane

H H
H C C H
H H
ethane

H H
H H
H H H H
C C C C

C –– H bond formed
H H by sp3–s overlap
H H
C –– C bond formed
by sp3–sp3 overlap

▲ Figure 1.8
An orbital picture of ethane. The C ¬ C bond is formed by sp3–sp3 overlap, and each C ¬ H bond is formed by sp3–s
overlap. (The smaller lobes of the sp3 orbitals are not shown.) As a result, both carbons are tetrahedral and all
bond angles are ∼109.5°.
 Rule : If two or three pairs of electrons form a multiple bond between two
atoms, the first bond is a sigma bond formed by a hybrid orbital. The sec-
ond bond is a pi bond, consisting of two lobes above and below the sigma
bond, formed by two unhybridized p orbitals (see the structure of ethylene).
The third bond of a triple bond is another pi bond, perpendicular to the first
pi bond.

H H
C C ethene
THE BONDS IN ETHENE ethylene
H H
an unhybridized
p orbital

p p p hybridization p
sp2 sp2 sp2
s
3 hybrid orbitals are formed
3 orbitals are hybridized

a.
b. p the p orbital is perpendicular
120° to the plane defined by the
sp2 orbitals ◀ Figure 1.10
sp2
(a) The three degenerate sp2 orbitals lie in
a plane, oriented 120° from each other.
(The smaller lobes of the sp2 orbitals are
not shown.)
sp2 sp2 (b) The unhybridized p orbital is
top view side view perpendicular to this plane.

a. s bond formed b. the p bond’s 2 electrons

by sp2–s overlap can be found anywhere in
H H the purple regions

H H
C C C C
H H
p bond s bond
H s bond formed by H
sp2–sp2 overlap
the 2 p orbitals are
parallel to each other
▲ Figure 1.11
(a) One C ¬ C bond in ethene is a s bond formed by sp2–sp2 overlap, and the C ¬ H bonds are s bonds
formed by sp2–s overlap.
(b) The second C ¬ C bond is a p bond formed by side-to-side overlap of a p orbital of one carbon with a
p orbital of the other carbon. The two p orbitals are parallel to each other.

a double bond H 121.7° H

consists of H H
one s bond and C C 116.6° C C
one p bond ∼118°
∼121°
H 1.33 Å H H H
perspective formula
 THE BONDS IN ETHYNE
H C C H
ethyne
acetylene

2 orbitals are left

unhybridized

p p p hybridization p p
sp sp
s
2 hybrid orbitals are formed
2 orbitals are hybridized

p
sp
▲ Figure 1.13
The two sp orbitals point in opposite
directions. The two unhybridized p orbitals
are perpendicular to each other and to the
sp orbitals. (The smaller lobes of the sp
p sp orbitals are not shown.)

the purple p orbitals

a. s bond formed by b. are perpendicular to
180° sp–s overlap the blue p orbitals
H
C
H C C H C
H
s bond formed by
sp–sp overlap

▲ Figure 1.14
(a) The C ¬ C S bond in ethyne is formed by sp–sp overlap, and the C ¬ H bonds are formed by sp–s overlap.
The carbon atoms and the atoms bonded to them form a straight line.
(b) The two carbon–carbon P bonds are formed by side-to-side overlap of the two p orbitals of one carbon
with the two p orbitals of the other carbon.

180°
H
C
H C C H
C
a triple bond
H consists of one 1.20 Å
s bond and perspective formula
two p bonds

▲ Figure 1.15
The triple bond has an electron-dense region
above and below and in front of and in back
of the internuclear axis of the molecule.
 THE BONDS IN THE METHYL CATION, THE
1.10 METHYL RADICAL, AND THE METHYL ANION
Not all carbon atoms form four bonds. A carbon with a positive charge, a negative charge, or an
unpaired electron forms only three bonds. Now we will see the orbitals that carbon uses when it
forms three bonds.

The Methyl Cation ( + CH3) The carbon in + CH3 is sp2 hybridized.

The positively charged carbon in the methyl cation is bonded to three atoms, so it hybridizes
three orbitals—an s orbital and two p orbitals. Therefore, it forms its three covalent bonds using
sp2 orbitals. Its unhybridized p orbital remains empty. The positively charged carbon (and the
three atoms bonded to it) lie in a plane. The unhybridized p orbital stands perpendicular to
the plane.
Representations of Methyl Cation

empty p orbital is
perpendicular to CH3 plane

bond formed by H
sp2–s overlap
H C+
H

angled side view top view

+CH ball-and-stick models
3

The Methyl Radical ( # CH3) The carbon in ~CH3 is sp2 hybridized.

The carbon atom in the methyl radical is also sp2 hybridized. The methyl radical, though, has one
more electron than the methyl cation. That electron is unpaired, and it resides in the p orbital, with
half of the electron density in each lobe. Although the methyl cation and the methyl radical have
similar ball-and-stick models, the potential maps are quite different because of the additional elec-
tron in the methyl radical.

Representations of the Methyl Radical

p orbital contains the

unpaired electron

bond formed by H
sp2–s overlap
H C
H

angled side view top view

CH3 ball-and-stick models
 -
The Methyl Anion (≠ CH3) The carbon in ≠
-
CH3 is sp3 hybridized.

The negatively charged carbon in the methyl anion has three pairs of bonding electrons
and one lone pair. Four pairs of electrons are farthest apart when the four orbitals contain-
ing the  ­bonding and lone-pair electrons point toward the corners of a tetrahedron. Thus, the
negatively charged carbon in the methyl anion is sp3 hybridized. In the methyl anion, three of
carbon’s sp3 orbitals each overlap the s orbital of a hydrogen, and the fourth sp3 orbital holds
the lone pair.

Representations of the Methyl Anion

lone-pair electrons
are in an sp3 orbital

bond formed by
sp3-s overlap
C
H H
H
−
CH3 ball-and-stick model