I.

Structure and
Bonding (cont.)
Chem211E Organic Chemistry
Engr. KBDimalanta

Source: https://commons.wikimedia.org/wiki/File:Dichloran.gif
Source: https://www.ch.ic.ac.uk/local/organic/pericyclic/p1_electro_22.html
 I. Structure
& Bonding (cont.)
Chem 211E: Organic Chemistry
Engr. KBDimalanta
REVIEW: The
▪ Resonance structures or resonance forms are representations
Atomic Structure of two Lewis structures having the same arrangement of atoms
but different arrangement of electrons.
1. Lewis Structures
➢ A resonance hybrid represents a structure of the composite
2. Resonance of both resonance forms. It shows characteristics of both
resonance structures.
3. Molecular Shapes
and Saturation ➢ A molecule with two or more resonance structures is said to
be resonance stabilized.
4. Hybridization

5. Bond Length &

Bond Strength
▪ Each resonance structure implies that electron pairs are localized
in bonds or on atoms. In reality, resonance allows certain
6. Electronegativity electron pairs to be delocalized over two or more atoms, and this
and Polarity
delocalization of electron density adds stability to the molecule.
REVIEW: The
EXAMPLE:
Atomic Structure

1. Lewis Structures Let’s draw the resonance structure of an anion (𝐻𝐶𝑂𝑁𝐻)−

2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
The principles of the resonance theory are as follows:
Atomic Structure ✓ Resonance structures are imaginary, not real. The REAL
1. Lewis Structures
structure, or the resonance hybrid, is a composite of all the
different forms.
2. Resonance
✓ Resonance structures are not in equilibrium with each other. There
3. Molecular Shapes is no movement of electrons from one form to another. When two
and Saturation resonance forms are non-equivalent, the actual structure of the
4. Hybridization
resonance hybrid is closer to the more stable form.
✓ A resonance hybrid is more stable than any individual resonance
5. Bond Length &
Bond Strength
structure. Resonance leads to stability. The larger the number of
resonance forms, the more stable a substance is because
6. Electronegativity electrons are distributed over a larger part of the molecule and are
and Polarity
closer to more nuclei.
REVIEW: The
The principles of the resonance theory (cont.):
Atomic Structure ✓ Resonance structures obey normal rules of valency. The
1. Lewis Structures
resonance forms follow the octet rule.
✓ Resonance structures are NOT isomers. Two isomers differ in the
2. Resonance
arrangement of both atoms and electrons, whereas resonance
3. Molecular Shapes structures differ only in the arrangement of electrons.
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
Atomic Structure Rule 1. Two resonance structures differ in the position of multiple
1. Lewis Structures bonds and nonbonded electrons. The placement of atoms
2. Resonance
and single bonds always stays the same.

3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
Rule 2. Two resonance structures must have the same number of
Atomic Structure unpaired electrons.
1. Lewis Structures

2. Resonance

3. Molecular Shapes
and Saturation Rule 3. Resonance structures must be valid Lewis structures.
4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
▪ The curved arrow notation shows the movement of an electron
Atomic Structure pair in the resonance structure.
1. Lewis Structures
➢ The tail of the arrow denotes the initial location of an electron
pair, either in a bond or lone pair.
2. Resonance
➢ The head points where the electron pair will be transferred.
3. Molecular Shapes
and Saturation A curved arrow always begins at an electron
4. Hybridization pair and ends at an atom or a bond.

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
EXAMPLE: Follow the curved arrows to draw a second resonance
Atomic Structure structure for the ions shown below:
1. Lewis Structures
1. .

2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization
2. .
5. Bond Length &
Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
▪ The resonance hybrid is the composite of all possible resonance
Atomic Structure structures. It is more stable than any individual resonance structure
because it delocalizes electron density over a larger volume.
1. Lewis Structures
▪ Each resonance structure contributes equally to the resonance
2. Resonance hybrid. When two resonance structure are different, the “better”
resonance form will be the major contributor and other forms are
3. Molecular Shapes
and Saturation minor contributors.
➢ The “better” resonance structure contains more bonds and
4. Hybridization
fewer charges.
5. Bond Length &
Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
EXAMPLE: Determine the resonance hybrid of the two resonance
Atomic Structure structures as shown below:
1. Lewis Structures

2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
EXAMPLE (cont.):
Atomic Structure
• Double bond position. Structure A and B
1. Lewis Structures has a 𝐶−𝑂 and 𝐶−𝑁 double bond,
respectively. A dashed line in the hybrid
2. Resonance
indicates partial double bond character
3. Molecular Shapes between these atoms.
and Saturation

4. Hybridization • Location of the charge. A negative charge

resides on different atoms in A and B.
5. Bond Length & The 𝛿 −, partial negative charge, indicates
Bond Strength
that the charge is delocalized on the 𝑁
6. Electronegativity and 𝑂 atoms in the hybrid.
and Polarity
REVIEW: The
OTHER EXAMPLES:
Atomic Structure

1. Lewis Structures

2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
OTHER EXAMPLES:
Atomic Structure

1. Lewis Structures

2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
▪ Refers to the bond length and bond angle that define a molecule’s
Atomic Structure structure.
1. Lewis Structures

2. Resonance ➢ the average distance, reported in picometer (pm) or angstrom (Å),

between the center of two bonded nuclei.
3. Molecular Shapes
and Saturation Bond length decreases across a row of the p. table as the size of the
atom decreases.
4. Hybridization

5. Bond Length &

Bond Strength
Bond length increases down a column of the p. table as the size of
6. Electronegativity an atom increases.
and Polarity
REVIEW: The
Average bond lengths:
Atomic Structure

1. Lewis Structures

2. Resonance

3. Molecular Shapes
and Saturation Source: Smith (2010)

4. Hybridization

5. Bond Length & ➢ determines the shape around any atom bonded to two other
Bond Strength atoms
▪ The bond angle/shape around a given atom can be determined by
6. Electronegativity
examining the groups, atoms or lone pair of electrons, surrounding it. After
and Polarity
which we consider the valence shell electron pair repulsion (VSEPR)
theory.
REVIEW: The
(cont.)
Atomic Structure The bond angle involving atoms in the second-row, of the periodic
1. Lewis Structures
table, has only three possible arrangements that are dependent on
the number of groups surrounding it.
2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length & Source: Smith (2010)

Bond Strength

6. Electronegativity
In drawing a three-dimensional geometry on two-dimensions, a solid
and Polarity line is used for a bond in the plane; a wedge is used for a bond in
front of the plane; a dashed line is used for a bond behind the plane.
REVIEW: The
(cont.)
Atomic Structure Acceptable and equivalent drawings of 3-D figures on 2-D:
1. Lewis Structures

2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
(cont.)
Atomic Structure
❖ Any atom surrounded by only two groups is linear and has a bond
1. Lewis Structures
angle of 180°.
2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
(cont.)
Atomic Structure

1. Lewis Structures
❖Any atom surrounded by three groups is trigonal planar and has
bond angles of 120°.
2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
(cont.)
Atomic Structure

1. Lewis Structures
❖Any atom surrounded by four groups is tetrahedral and has bond
angles of approximately 109.5°.
2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
Saturated hydrocarbons → ALL single bonds
Atomic Structure Unsaturated hydrocarbons → at least ONE multiple bonding
1. Lewis Structures

2. Resonance
❖Square planar.
3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
REVIEW: The
Atomic Structure ❖Trigonal pyramid
1. Lewis Structures

2. Resonance

3. Molecular Shapes
and Saturation
❖Bent
4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
 1. CONDENSED STRUCTURES
REVIEW: The
Atomic Structure • This type of structure is often used on compounds with atoms
bonded in chain. It is interpreted from the left side of the molecule
1. Lewis Structures
and considers carbon atoms represented in tetravalent geometry.
2. Resonance

3. Molecular Shapes Below are conventions in writing the condensed structures:

and Saturation ✓ All the atoms are drawn. The two-electron bond lines are
4. Hybridization
omitted.
✓ Atoms are drawn next to the atom to which it is bonded.
5. Bond Length &
Bond Strength
✓ Parenthesis are used around similar groups bonded to the
same atom.
6. Electronegativity ✓ Lone pairs are omitted.
and Polarity
 EXAMPLES:
REVIEW: The
Atomic Structure

1. Lewis Structures = 𝐶𝐻3 𝐶𝐻𝑂 = 𝐶𝐻3 𝐶𝑂𝐶𝐻3

2. Resonance

3. Molecular Shapes
and Saturation
= 𝐶𝐻3 𝐶𝑂2 𝐻
= 𝐶𝐻3 𝐶𝑂2 𝐶𝐻3
4. Hybridization

5. Bond Length &

Bond Strength
= (𝐶𝐻3 )3 CH
6. Electronegativity
and Polarity
= 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻3
= 𝐶𝐻3 (𝐶𝐻2 )2 𝐶𝐻3
 EXAMPLES:
REVIEW: The
Atomic Structure
=
1. Lewis Structures
= 𝐶𝐻3 𝐶𝐻2 𝐶𝐻(𝐶𝐻3 )𝐶𝐻2 𝐶𝐻3
2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength
→ 𝐶𝐻3 𝐶𝐻 = 𝐶𝐻𝐶𝐻3 =
6. Electronegativity
and Polarity → 𝐶𝐻3 𝐶𝐻𝐶𝐻𝐶𝐻3
=
 2. SKELETAL STRUCTURES
REVIEW: The
Atomic Structure • This type of structure can be used to compounds with atoms
bonded in chain and ring. Carbon chains are drawn as zigzag
1. Lewis Structures
while rings are drawn as polygons.
2. Resonance

3. Molecular Shapes Below are conventions in writing/drawing skeletal structures:

and Saturation ✓ Assume there is a carbon atom at the junction of any two lines
4. Hybridization
or at the end of any line.
✓ Assume there are enough hydrogens around each carbon to
5. Bond Length & make it tetravalent.
Bond Strength
✓ Draw all heteroatoms and the hydrogens directly bonded to
6. Electronegativity them.
and Polarity
 EXAMPLES:
REVIEW: The
Atomic Structure
= 𝐶𝐻3 (𝐶𝐻2 )4 𝐶𝐻3 =
1. Lewis Structures

2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization
= 𝑛𝑜 𝑐𝑜𝑛𝑑𝑒𝑛𝑠𝑒𝑑 𝑠𝑡𝑟𝑢𝑐𝑡𝑢𝑟𝑒 =

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity =
 2. SKELETAL STRUCTURES (cont.)
REVIEW: The
Atomic Structure
Remember!
1. Lewis Structures
When heteroatoms are bonded to a carbon skeleton, the heteroatom
2. Resonance is joined directly to the carbon to which is it bonded, with no 𝐻 atoms
3. Molecular Shapes in between. In contrast, when carbon attachments are bonded to a
and Saturation carbon skeleton, the 𝐻 atoms will be drawn to the right of the carbon
to which they are bonded regardless of the location.
4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity
 3. SKELETAL ATOMS w/ CHARGED ATOMS
REVIEW: The
Atomic Structure • The skeletal structure omits hydrogen atoms and lone pairs.
1. Lewis Structures
Below are conventions in writing/drawing skeletal structures w/
2. Resonance charged atoms:
3. Molecular Shapes ✓ A charge on a carbon atom takes the place of one hydrogen
and Saturation atom.
4. Hybridization
✓ The charge determines the number of lone pairs. Negatively
charged carbon atoms have one lone pair and positively
5. Bond Length & charged carbon atoms have none.
Bond Strength

6. Electronegativity
and Polarity
 EXAMPLES:
REVIEW: The
Atomic Structure

1. Lewis Structures =

2. Resonance

3. Molecular Shapes
and Saturation

4. Hybridization = =
5. Bond Length &
Bond Strength

6. Electronegativity
and Polarity
 EXAMPLES with heteroatoms:
REVIEW: The
Atomic Structure
Neutral 𝑂 atom owns six electrons:
1. Lewis Structures = • Two bonds (four bonding
electrons)
2. Resonance • Two lone pairs (four
unshared electrons)
3. Molecular Shapes
and Saturation

4. Hybridization Positively charged 𝑂 atom owns five

= electrons:
5. Bond Length & • Three bonds (six bonding
Bond Strength electrons)
• One lone pair (two unshared
6. Electronegativity electrons)
and Polarity
REVIEW: The 1. McMurry, J. (2008). Organic Chemistry, 7th Edition. Thomson
Atomic Structure
Brooks/Cole, USA.
1. Lewis Structures
2. Smith, J.G. (2010). Organic Chemistry, 3rd Edition. McGraw
2. Resonance Hill, USA.
3. Molecular Shapes
and Saturation

4. Hybridization

5. Bond Length &

Bond Strength

6. Electronegativity
and Polarity