Organic 

Chemistry
William H. Brown
Christopher S. Foote
Brent L. Iverson
1-1
Covalent
Bonding &
Shapes of
Molecules
Chapter 1

1-2
Organic Chemistry
 The study of the compounds of carbon
 Over 10 million compounds have been
identified
• about 1000 new ones are identified each day!
 C is a small atom
• it forms single, double, and triple bonds
• it is intermediate in electronegativity (2.5)
• it forms strong bonds with C, H, O, N, and some
metals

1-3
Schematic View of an Atom
• a small dense
nucleus, diameter 10-
14 - 10-15 m, which

contains positively
charged protons and
most of the mass of
the atom
• an extranuclear
space, diameter 10-10
m, which contains
negatively charged
electrons

1-4
Electron Configuration of Atoms
 Electrons are confined to regions of space
called principle energy levels (shells)
• each shell can hold 2n2 electrons (n =
1,2,3,4......)
Number of Relative Energies
Electrons Shell of Electrons
Shell Can Hold in These Shells
4 32 higher
3 18
2 8
1 2
lower

1-5
Electron Configuration of Atoms
 Shells are divided into subshells called
orbitals, which are designated by the
letters s, p, d, f,........
• s (one per shell)
• p (set of three per shell 2 and higher)
• d (set of five per shell 3 and higher) .....

Shell Orbitals Contained in That Shell

3 3s, 3p x , 3py, 3pz, plus five 3d orbitals
2 2s, 2p x , 2py, 2pz
1 1s

1-6
Electron Configuration of Atoms
 Aufbau Principle:
• orbitals fill in order of increasing energy from
lowest energy to highest energy
 Pauli Exclusion Principle:
• only two electrons can occupy an orbital and
their spins must be paired
 Hund’s Rule:
• when orbitals of equal energy are available but
there are not enough electrons to fill all of
them, one electron is added to each orbital
before a second electron is added to any one of
them

1-7
Electron Configuration of Atoms
 The pairing of electron spins

1-8
Electron Configuration of Atoms
 Table 1.3 The Ground-State Electron
Configuration of Elements 1-18

1-9
Lewis Dot Structures
 Gilbert N. Lewis
 Valence shell:
• the outermost occupied electron shell of an
atom
 Valence electrons:
• electrons in the valence shell of an atom; these
electrons are used to form chemical bonds and
in chemical reactions
 Lewis dot structure:
• the symbol of an element represents the
nucleus and all inner shell electrons
• dots represent valence electrons
1-10
Lewis Dot Structures
 Table 1.4 Lewis Dot Structures for Elements 1-18
1A 2A 3A 4A 5A 6A 7A 8A
H. He :
. . . . . :
Li . Be : B: C : .N : :O. : :F
: : :Ne
: :
. . . . . :
Na. Mg : Al : Si : .P: :S. : :Cl
: : :Ar
: :

1-11
Lewis Model of Bonding
 Atoms bond together so that each atom
acquires an electron configuration the same
as that of the noble gas nearest it in atomic
number
• an atom that gains electrons becomes an anion
• an atom that loses electrons becomes a cation
• the attraction of anions and cations leads to the
formation of ionic solids
• an atom may share electrons with one or more
atoms to complete its valence shell; a chemical
bond formed by sharing electrons is called a
covalent bond
• bonds may be partially ionic or partially covalent;
these bonds are called polar covalent bonds
1-12
Electronegativity
 Electronegativity:
• a measure of an atom’s attraction for the
electrons it shares with another atom in a
chemical bond
 Pauling scale
• generally increases left to right in a row
• generally increases bottom to top in a column

1-13
Formation of Ions
 A rough guideline:
• ions will form if the difference in
electronegativity between interacting atoms is
1.9 or greater
• example: sodium (EN 0.9) and fluorine (EN 4.0)
• we use a single-headed (barbed) curved arrow
to show the transfer of one
•• ••
+
electron
-
from Na to
• • ••
••
Na + F Na F
F •• ••

• in
Na(1s2 forming Na2+2s
2s 22p63s1 ) + F(1s F-2,2pthe
5
)
single s 2electron
Na+3(1s from
2s22p6) + F-(1s2 Na
2s2 2p6 )
is transferred to the partially filled valence
shell of F
1-14
Covalent Bonds
 The simplest covalent bond is that in H2
• the single electrons from each atom combine to
form an electron pair
HΔ + •H H-H ΔH 0 = -435 kJ (-104 kcal)/m ol

• the shared pair functions in two ways

simultaneously; it is shared by the two atoms
and fills the valence shell of each atom
 The number of shared pairs
• one shared pair forms a single bond
• two shared pairs form a double bond
• three shared pairs form a triple bond

1-15
Polar and Nonpolar Covalent
Bonds
 Although all covalent bonds involve
sharing of electrons, they differ widely in
the degree of sharing
 We divide covalent bonds into
• nonpolar covalent bonds
• polar covalent bonds

Difference in
Electronegativity
Between Bonded Atoms Type of Bond
Less than 0.5 Nonpolar covalent
0.5 to 1.9 Polar covalent
Greater than 1.9 Ions form

1-16
Polar and Nonpolar Covalent
Bonds
• an example of a polar covalent bond is that of
H-Cl
• the difference in electronegativity between Cl
and H is 3.0 - 2.1 = 0.9
• we show polarity by using the symbols  + and
 -, or by using an arrow with the arrowhead
pointing toward the negative end and a plus
sign on the tail of the arrow at the positive end
Δ+ δ-
H Cl H Cl

1-17
Polar Covalent Bonds
 Bond dipole moment (m ):
• a measure of the polarity of a covalent bond
• the product of the charge on either atom of a
polar bond times the distance between the
nuclei
• Table 1.7 shows average bond dipole moments
of selected covalent bonds
Bond Bond Bond
Dipole Dipole Dipole
Bond (D) Bond (D) Bond (D)

H-C 0.3 C-F 1.4 C-O 0.7

H-N 1.3 C-Cl 1.5 C=O 2.3
H-O 1.5 C-Br 1.4 C-N 0.2
H-S 0.7 C-I 1.2 --
C=N 3.5
1-18
Lewis Structures
 To write a Lewis structure
• determine the number of valence electrons
• determine the arrangement of atoms
• connect the atoms by single bonds
• arrange the remaining electrons so that each
atom has a complete valence shell
• show a bonding pair of electrons as a single line
• show a nonbonding pair of electrons as a pair of
dots
• in a single bond atoms share one pair of
electrons, in a double bond they share two pairs
of electrons, and in a triple bond they share
three pairs of electrons
1-19
Lewis Structures - Table 1.3
H
H-O-H H-N-H H-C-H H-Cl
H H
H2 O (8) NH3 (8) CH4 (8) HCl (8)
Water Ammonia Methane Hydrogen chloride
H H H O
C C H-C C-H C O H C H
O O
H H H
C2 H4 (12) C 2H2 (10) CH2O (12) H2CO3 (24)
Ethylene Acetylene Formaldehyde Carbonic acid
 In neutral molecules
• hydrogen has one bond
• carbon has 4 bonds and no lone pairs
• nitrogen has 3 bonds and 1 lone pair
• oxygen has 2 bonds and 2 lone pairs
• halogens have 1 bond and 3 lone pairs
1-20
Formal Charge
 Formal charge: the charge on an atom in a
molecule or a polyatomic ion
 To derive formal charge
1. write a correct Lewis structure for the
molecule or ion
2. assign each atom all its unshared (nonbonding)
electrons and one-half its shared (bonding)
electrons
3. compare this number with the number of
valence Number
electrons
of in the neutral, unbonded
Formal All One half of
atom = valence electrons unshared + all shared
charge in the neutral,
unbonded atom electrons electrons

1-21
Formal Charge
 Example: Draw Lewis structures, and show which
atom in each bears the formal charge
- - 2-
(a) NH2 (b) HCO3 (c) CO3

+ - -
(d) CH3 NH3 (e) HCOO (f) CH3COO

1-22
Exceptions to the Octet Rule
 Molecules containing atoms of Group 3A
elements, particularly boron and aluminum
: 6 electrons in the
:F:

:
valence shells of boron :Cl :
and aluminum
: :

: :
:F B :Cl Al
:F : :Cl :
:

:
Boron trifluoride Aluminum chloride

1-23
Exceptions to the Octet Rule
 Atoms of third-period elements have 3d
orbitals and may expand their valence
shells to contain more than 8 electrons
• phosphorus may have up : to 10
: :Cl: : : O:
: : Cl : :
: Cl
: :
CH3 -P- CH3 : P : H- :O-P- O-H
:
CH3 : Cl
: Cl
: : O-H
:
Trimethyl- Phosphorus Phosphoric
phosphine pentachloride acid

1-24
Exceptions to the Octet Rule
• sulfur, another third-period element, forms
compounds in which its valence shell contains
8, 10, or 12 electrons
: O: : O:
: : :
H-S-H
: CH3 -S-CH
: 3 H-O-S-O-H
: :
: O:

Hydrogen Dimethyl Sulfuric

sulfide sulfoxide acid

1-25
Functional Groups
 Functional group: an atom or group of
atoms within a molecule that shows a
characteristic set of physical and chemical
properties
 Functional groups are important for three
reason; they are
1. the units by which we divide organic
compounds into classes
2. the sites of characteristic chemical reactions
3. the basis for naming organic compounds

1-26
Alcohols
 contain an -OH (hydroxyl)
hydroxyl group
: HH
-C-O-H
: H-C-C-O-H
HH
Functional Ethanol
group (an alcohol)

 Ethanol may also be written as a

condensed structural formula
CH3 -CH2 -OH or CH3 CH2 OH

1-27
Alcohols
• alcohols are classified as primary (1°),
secondary (2°), or tertiary (3°) depending on the
number of carbon atoms bonded to the carbon
bearing theCH
-OH
3 group H CH3
CH3 -C-OH CH3 -C-OH CH3 -C-OH
CH3 CH3 CH3
A 1° alcohol A 2° alcohol A 3° alcohol

1-28
Alcohols
• there are two alcohols with molecular formula
C3H8O
HHH
H-C-C-C-O-H or CH3 CH2CH2 OH
H HH a 1° alcohol

H
HOH OH
H C-C-C-H or CH3CHCH3
HH H a 2° alcohol

1-29
Amines
 group an sp3-hybridized
contain an amino group;
nitrogen bonded to one, two, or three
carbon atoms
• an amine may by 1°, 2°, or 3°

:
:

:
CH3 N H CH3 N H CH3 N CH3
H CH3 CH3
Methylamine Dimethylamine Trimethylamine
(a 1° amine) (a 2° amine) (a 3° amine)

1-30
Aldehydes and Ketones
 contain a carbonyl (C=O) group
O O O O
C H CH3-C-H C CH3 -C-CH3
Functional Acetaldehyde Functional Acetone
group (an aldehyde) group (a ketone)

1-31
Carboxylic Acids
 contain a carboxyl (-COOH) group
O :O::
C O H CH3 -C-O-H
: or CH3COOH or CH3 CO2 H
Functional Acetic acid
group (a carboxylic acid)

1-32
Carboxylic Esters
 Ester: a derivative of a carboxylic acid in
which the carboxyl hydrogen is replaced
by a carbon group
O : O: :
C O CH3 -C-O-CH
: 2 -CH3

Functional Ethyl acetate

group (an ester)

1-33
Carboxylic Amide
 Carboxylic amide,
amide commonly referred to as
an amide:
amide a derivative of a carboxylic acid
in which the -OH of the -COOH group is
replaced by an amine
O O
C N CH3 -C-N-H
H
Functional Acetamide
group (a 1° amide)

• the six atoms of the amide functional group lie

in a plane with bond angles of approximately
120°

1-34
VSEPR
 Based on the twin concepts that
• atoms are surrounded by regions of electron
density
• regions of electron density repel each other
H
:
4 regions of e- density
C N O
(tetrahedral, 109.5°) H H H
H H H H H

H H H : H H
3 regions of e- density
(trigonal planar, 120°) C C C :
O C N
:
H H H H
: :
2 regions of e- density
:O C O
: H C C H H C N
(linear, 180°)

1-35
VSEPR Model
 Example: predict all bond angles for these
molecules and ions
(a) NH4 + (b) CH3 NH2 (d) CH3 OH
(e) CH3 CH=CH2 (f) H2 CO3 (g) HCO3 -
(h) CH3 CHO (i) CH3COOH (j) BF4 -

1-36
Polar and Nonpolar Molecules
 To determine if a molecule is polar, we
need to determine
• if the molecule has polar bonds
• the arrangement of these bonds in space
 Molecular dipole moment (m ): the vector
sum of the individual bond dipole moments
in a molecule
• reported in debyes (D)

1-37
Polar and Nonpolar Molecules
 these molecules have polar bonds, but
each has a zero dipole moment

F Cl

O C O B F C
F Cl Cl
Cl
Carbon dioxide Boron trifluorie Carbon tetrachlorie
Δ=0D Δ=0D Δ=0D

1-38
Polar and Nonpolar Molecules
 these molecules have polar bonds and are
polar molecules
irection O N irection
of ip ole of ip ole
H H H H
m om ent m om ent
H
Water Am m onia
Δ = 1.85D Δ = 1.47D

1-39
Polar and Nonpolar Molecules
• formaldehyde has polar bonds and is a polar
molecule
irection O
of ip ole C
m om ent H H
Formaldehyde
Δ = 2.33 D

1-40
Resonance
 For many molecules and ions, no single
Lewis structure provides a truly accurate
representation
-
O O
H3 C C and H3 C C
O O
-
Ethanoate ion
(acetate ion)

1-41
Resonance
 Linus Pauling - 1930s
• many molecules and ions are best described by
writing two or more Lewis structures
• individual Lewis structures are called
contributing structures
• connect individual contributing structures by
double-headed (resonance) arrows
• the molecule or ion is a hybrid of the various
contributing structures

1-42
Resonance
 Examples: equivalent contributing structures
: : : :
:O:- O: : O: -
O:
:N :N CH3 C CH3 C
: :
O :O
: :- : :
O :O
: :-
Nitrite ion Acetate ion
(equivalent contributing (equivalent contributing
structures) structures)

1-43
Resonance
 Curved arrow: a symbol used to show the
redistribution of valence electrons
 In using curved arrows, there are only two
allowed types of electron redistribution:
• from a bond to an adjacent atom
• from an atom to an adjacent bond
 Electron pushing is a survival skill in
organic chemistry
• learn it well!

1-44
Resonance
 All contributing structures must
1. have the same number of valence electrons
2. obey the rules of covalent bonding
• no more than 2 electrons in the valence shell of
H
• no more than 8 electrons in the valence shell of
a 2nd period element
• 3rd period elements, such as P and S, may have
up to 12 electrons in their valence shells
3. differ only in distribution of valence electrons;
the position of all nuclei must be the same
4. have the same number of paired and unpaired
electrons
1-45
Resonance
 The carbonate ion, for example
• a hybrid of three equivalent contributing
structures
• the negative charge is distributed equally
among the three oxygens

1-46
Resonance
 Preference 1: filled valence shells
• structures in which all atoms have filled
valence shells contribute more than those with
one or more unfilled valence shells
+ •• +
CH3 O C H CH3 O C H
•• ••

H H
Greater contribution; Lesser contribution;
both carbon and oxygen havecarbon has only 6 electrons
complete valence shells in its valence shell

1-47
Resonance
 Preference 2: maximum number of
covalent bonds
• structures with a greater number of covalent
bonds contribute more than those with fewer
covalent bonds
+ •• +
CH3 ••
O C H CH3 ••
O C H

H H
Greater contribution Lesser contribution
(8 covalent bonds) (7 covalent bonds)

1-48
Resonance
 Preference 3: least separation of unlike
charge
• structures with separation of unlike charges
:
contributeO:less than those with
:O: - no charge

:
separation
CH3 -C-CH3 CH3 -C-CH3
Greater contributionLesser contribution
(no separation of (separation of unlike
unlike charges) charges)

1-49
 Resonance
 Preference 4: negative charge on the more
electronegative atom
• structures that carry a negative charge on the
more electronegative atom contribute more
than those with the negative charge on the less
electronegative atom
O O O
(1) C (2)
C C
H3 C CH3 H3 C CH3 H3 C CH3
(a) (b) (c)
Lesser Greater Should not
contribution contribution be drawn

1-50
Quantum or Wave Mechanics
 Albert Einstein: E = hn (energy is quantized)
• light has particle properties
 Louis deBroglie: wave/particle duality
h
Δ = mν
 Erwin Schrödinger: wave equation
• wave function,  : a solution to a set of equations
that depicts the energy of an electron in an atom
• each wave function is associated with a unique
set of quantum numbers
• each wave function occupies three-dimensional
space and is called an orbital
•  2 is the probability of finding an electron at a
given point in space
1-51
Shapes of 1s and 2s Orbitals
 Probability distribution ( 2) for 1s and 2s
orbitals showing an arbitrary boundary
surface containing about 95% of the
electron density

1-52
Shapes of a Set of 2p Atomic
Orbitals
 Three-dimensional shapes of 2p atomic
orbitals

1-53
Molecular Orbital Theory
 Electrons in atoms exist in atomic orbitals
 Electrons in molecules exist in molecular
orbitals (MOs)
 Using the Schrödinger equation, we can
calculate the shapes and energies of MOs

1-54
Molecular Orbital Theory
 Rules:
• combination of n atomic orbitals
(mathematically adding and subtracting wave
functions) gives n MOs (new wave functions)
• MOs are arranged in order of increasing energy
• MO filling is governed by the same rules as for
atomic orbitals:
• Aufbau principle: fill beginning with LUMO
• Pauli exclusion principle: no more than 2e- in
a MO
• Hund’s rule: when two or more MOs of
equivalent energy are available, add 1e- to
each before filling any one of them with 2e-
1-55
Molecular Orbital Theory
 Terminology
• ground state = lowest energy state
• excited state = NOT lowest energy state
•  = sigma bonding MO
• * = sigma antibonding MO
• p = pi bonding MO
• p* = pi antibonding MO
• HOMO = highest occupied MO
• LUMO = lowest unoccupied MO

1-56
Molecular Orbital Theory
 Sigma 1s bonding and antibonding MOs

1-57
Molecular Orbital Theory
• MO energy diagram for H2: (a) ground state and
(b) lowest excited state

1-58
Molecular Orbitals
• computed sigma bonding and antibonding MOs
for H2

1-59
Molecular Orbitals
 pi bonding and antibonding MOs

1-60
Molecular Orbitals
• computed pi bonding and antibonding MOs for
ethylene

1-61
Molecular Orbitals
• computed pi bonding and antibonding orbitals
for formaldehyde

1-62
Hybrid Orbitals
 The Problem:
• bonding by 2s and 2p atomic orbitals would
give bond angles of approximately 90°
• instead we observe bond angles of
approximately 109.5°, 120°, and 180°
 A Solution
• hybridization of atomic orbitals
• 2nd row elements use sp3, sp2, and sp hybrid
orbitals for bonding

1-63
Hybrid Orbitals
 Hybridization of orbitals (L. Pauling)
• the combination of two or more atomic orbitals
forms a new set of atomic orbitals, called hybrid
orbitals
 We deal with three types of hybrid orbitals
sp3 (one s orbital + three p orbitals)
sp2 (one s orbital + two p orbitals)
sp (one s orbital + one p orbital)
 Overlap of hybrid orbitals can form two types
of bonds depending on the geometry of
overlap
 bonds are formed by “direct” overlap
p bonds are formed by “parallel” overlap
1-64
sp3 Hybrid Orbitals
• each sp3 hybrid
orbital has two lobes
of unequal size
• the sign of the wave
function is positive
in one lobe, negative
in the other, and zero
at the nucleus
• the four sp3 hybrid
orbitals are directed
toward the corners
of a regular
tetrahedron at
angles of 109.5°
1-65
sp3 Hybrid Orbitals
• orbital overlap pictures of methane, ammonia,
and water

1-66
sp2 Hybrid Orbitals
• the axes of the three sp2 hybrid orbitals lie in a
plane and are directed toward the corners of an
equilateral triangle
• the unhybridized 2p orbital lies perpendicular to
the plane of the three hybrid orbitals

1-67
Bonding in Ethylene

1-68
Bonding in Formaldehyde

1-69
sp Hybrid Orbitals
• two lobes of unequal size at an angle of 180°
• the unhybridized 2p orbitals are perpendicular
to each other and to the line created by the
axes of the two sp hybrid orbitals

1-70
Bonding in Acetylene, C2H2

1-71
Hybrid Orbitals
Groups Orbital Predicted Types of
Bonded Hybrid- Bond Bonds
to Carbon ization Angles to Carbon Example Name
HH
4 sp3 109.5° 4 sigma bonds H-C-C-H Ethane
HH

H H
sp 2
120° 3 sigma bonds
2 C C Ethylene
and 1 pi bond
H H

2 sp 180° 2 sigma bonds

H-C C-H Acetylene
and 2 pi bonds

1-72
Bond Lengths and Bond Strengths

Orbital Bond Length Bond Strength

Name Formula Bond Overlap (pm) [kJ (kcal)/mol]

HH C-C sp3 -sp 3 153.2 376 (90)

Ethane H-C-C-H
C-H sp3 -1s 111.4 422 (101)
HH

H H C-C sp2-sp2, 2p-2p 133.9 727 (174)

Ethylene C C
H H C-H sp 2-1s 110.0 464(111)

C-C sp-sp, two 2p-2p 121.2 966 (231)

Acetylene H-C C-H
C-H sp-1s 109.0 556 (133)

1-73
Covalent
Bonds &
Shapes of
Molecules
End Chapter 1
1-74