Introduction & Review:

Structure & Bonding

Chapter 1
• Pacific Yew contains a compound
within the bark that inhibits cell
growth and is useful in the
treatment of some cancers.

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Carbon forms the basis of compounds studied in
organic chemistry.
-small in size
-6p, 6e, (6n)
-4 valence electrons
-stable bonds
-potential for multiple bonds

Other atoms commonly found in these compounds

are H, N, O
The valence electrons are the electrons that interact to form bonds
with other atoms and create molecules.
Ionic bonding: (mostly metal/nonmetal)
Consider the formation of NaBr

Covalent bonding: (nonmetal atoms)

Consider H2
Lewis Structures:
Used to symbolize the covalent bonds and lone pairs present in a
molecule.
Ex.
 is a measure of an atom to pull electrons toward
itself when bonded to other atoms. The higher the value, the larger the
shift of electrons within the bond toward that nucleus.

Hydrogen Carbon Nitrogen Oxygen Fluorine Chlorine

The greater the difference, ΔX, between the atoms, the more
the bond becomes.
Ex.

These shifts in electron density can create polarity, or a dipole moment,

within a molecule.

dipole moment = charge x distance between atoms

 it is the difference between the number of valence electrons
an atom has when un-bonded compared to the number it ‘owns’ in the bonded
molecule.
Formal charge: #of valence e- - # of nonbonding e- -1/2 e- within bonds
Ex.
When looking at Lewis Structures, you will begin to
notice typical bonding arrangements around atoms
and non-typical, which lead to charges.
Resonance
• There are times when a compound cannot be
represented by a single Lewis structure; more than
one structure is used. These structures differ only in
the . These are called resonance
structures.
• The actual structure is somewhere between the
resonance forms and is called the
Ex. C6H6

Ex. NO3-
Rules:
• All atoms must remain in the
• Resonance forms differ only in the placement of their
or electrons
• Resonance forms must be valid Lewis structures &
obey the normal rules of valency ie. N, O, C, H cannot
have an expanded octet
• Highly atoms such as N, O and
halogens help to charge. The can hold a
negative charge, but will only carry a positive charge if
they already have an octet.
• Some examples:
Key to Drawing Resonance Structures

• Pushable electrons = unshared/lone pair e- & e- in

multiple bonds
• Receptors:
1. Atoms with a formal
2. Atoms that can tolerate a formal
3. Atoms which possess e- themselves

• The receptor must be next to the pushable

electrons. If the receptor is too far away, there is
no way for the electrons to get to the receptor.
Things to Remember:
1. Always push electrons(-ve charge), never push

2. Always push electrons away from centers of

& towards +ve charge
• The resonance method depends on delocalizing
charge
• Electrons (-ve charge) must be pushed away from
centers of relatively high electron density &
towards centers of relatively low electron density
Ex.
The arrows demonstrate the way the electrons are
shifted to create the second structure.

HA A-
• Remember: only electrons can move, not atoms
• The resonance hybrid is more stable than any
individual resonance form
• i.e.

• The larger the number of resonance forms, the

more stable the species will be
• Resonance forms of a compound do not have to be
equivalent
• Often resonance structures have
contributors
• Both are always considered but the major
contributor predominates & is used to describe
the compound
• To determine the major/minor contributors of a
resonance structure, verify the octet rule is respected
& where the charge resides
• The major contributor is identified as the one with the
maximum # of octets and the maximum # of bonds.
Ex. Formaldehyde
Condensed Formulas(Table 1-2, 1-3)

Bonds are not show between carbon atoms, but

hydrogens attached to carbon are listed beside each
carbon.
Other atoms are written with the formula following the
carbon to which they are attached.
Ex. Butane
Line Angle Formulas (Table 1-4)

• Rule 1: carbon atoms are not shown

It is assumed that a carbon atom is present at each
intersection of 2 lines & at the end of each line
• Rule 2: hydrogen atoms bonded to carbon are not
shown
Since carbon will normally form 4 bonds we mentally
supply the correct number of H’s for each carbon
• Ex. Butane
• Rule 3: atoms other than C & H are shown.
If those atoms bear hydrogen atoms as well, those are
also shown.
Ex. Acetone, ethanol, 3-methyl-3-pentanol
• Draw a line angle/skeletal structure for each of the following
compounds
Atomic Orbitals
• Wave functions represent the probability of finding
electrons in a specific region of space
• We treat electrons like standing waves
• a mathematical description of size, shape, and
orientation
• s,p,d,f orbitals
• In organic chemistry we only need to concentrate on
Figure 2-2: The 1s orbital
• p orbitals have a nodal plane
• Node – area of space where the probability of finding
electrons is almost zero

Figure 2-4: The 2p orbital

• When bonding within a molecule occurs, we have to shift our model
Hybridization:
Carbon’s 4 valence electrons living in s + p
IF C has 4 attached groups, the orbitals become 4 equivalent
hybridized each holding an electron that points out in geometry.
IF C has 3 attached groups, the orbitals become 3 equivalent
hybridized each holding an electron that points out in
geometry.
IF C has 2 attached groups, the orbitals become 2 equivalent
hybridized each holding an electron that points out in geometry.
Hybridization & Molecular Shapes
• Molecular shapes are related to hybridization of
central atom
• Hybridization: combination of atomic orbitals of the
same atom producing orbitals of lower energy
Only 3 general shapes are normally found in organic
molecules
3D Drawing
-use dashes and wedges to give perspective to the bonds with the
molecule
Bonds-Sigma(σ) and Pi(π)
SIGMA BONDS
• All single bonds are sigma (σ) bonds and are the result of an
overlap of orbitals located the nuclei
• Sigma bonds are quite and hard to disrupt
PI BONDS
• Pi (π) bonds result from the overlap of p orbitals of
two atoms
• Cannot exist if a σ bond is not already present
• It is always to the σ bond connecting the nuclei
• Occur in sp2 & sp hybridized atoms (double & triple bonds)
• These bonds are weaker and and more susceptible to
reaction
• Double bond – 4 electrons in the bonding region
between the nuclei
• First 2 form σ bond
• Second 2 form π bond(use the unhybridized p
orbital that remains on each carbon)

Ex. Ethene (ethylene)

• Triple bond – 6 electrons in the bonding region
between the nuclei
• First pair forms the σ bond
• 2nd & 3rd pairs form the π bond(uses the 2
unhybridized p orbitals on each carbon)

Ex. Ethyne (acetylene)

Molecular Orbitals
• M.O. are produced when atomic orbitals of different
atoms interact
• Produces bonding orbitals (when the orbital waves
constructively interfere with each other) and anti-
bonding orbitals(when the orbital waves destructively
interfere with each other)

Figure 2-8: H2 MO
Figures 2-6 & 2-7
• In the case of p orbitals, the overlap can take place in
two different forms: end to end or side to side
Figure 2-9
Bond Rotation
• Ex. Ethane CH3CH3
• Both carbons are sp3 hybridized & tetrahedral
• Rotation about the single bond results in many
possible conformations
• Ex. Butene CH3(CH)2CH2
• Rotation about single bonds is allowed but double
& triple bonds are rigid and cannot be twisted
• Because of the rigidity, compounds with double
bonds that have a different substituent
arrangement are different (different chemical &
physical properties) even tho they have the same
molecular formula
• Isomers
Isomerism
• Constitutional (or structural) Isomers
• Isomers that differ in their bonding sequence
• Stereoisomers
• Compounds that differ only in how their atoms are
oriented in space (3D arrangement)
• See Chapter 5
• Ex. Cis/trans (geometric) isomers