Organic Chemistry 211

Organic Chemistry, 9th Edition, L. G. Wade, Jr.

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 Chapter 1: Structure and Bonding
Organic Chemistry: Organic chemistry is the chemistry of carbon compounds.
Organic compounds are compounds that contain carbon.
Organic compounds: from living organisms (with a vital force)
Inorganic compounds: from minerals (without a vital force)

5-Fluorouracil, Tamiflu, Influenza Drug

Colon Cancer Drug

AZT, HIV Drug Elavil, Antidepressant

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 Remembering General Chemistry: Electronic Structure of the Atom

• An atom has a dense, positively charged nucleus surrounded by a cloud of electrons.

 Protons are positively charged.
 Neutrons have no charge.
negative charge ( )
 Electrons are negatively charged and located outside the nucleus.
 atomic number = # of protons positive charge ( )
 atomic number of carbon = 6
 Neutral carbon has six protons and six electrons.
neutral
 Most of the mass of the atom is due to the nucleus.
 Most of the volume of an atom is due to the electrons.

Isotopes : Isotopes are atoms with the same number of protons but a different number of neutrons.

•All Carbon Atoms Have the Same Atomic Number = # of protons

•Carbon Atoms Can Have Different Mass Numbers

• Mass Number = # of protons + # of neutrons

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 What Makes Carbon So Special?

• Atoms to the left of carbon give up electrons.

• Atoms to the right of carbon accept electrons.
• Carbon shares electrons.

Electronic Configurations of Atoms

• Valence electrons are electrons on the
outermost shell of the atom.

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 Electronic Configurations

• Aufbau principle: An electron goes into the atomic orbital with the lowest energy.

1s < 2s < 2p < 3s < 3p < 3d

• Pauli exclusion principle: No more than two electrons can be in an atomic orbital.
• Hund’s rule: An electron goes into an empty degenerate orbital rather than pairing up.

Atoms in the First Column of the Periodic Table Lose an Electron

An atom is most stable if its outer shell is either filled or contains 8 electrons.
Lithium achieve a filled outer shell by losing an electron.

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 Atoms on the Right Side of the Periodic Table Readily Gain an Electron

Ionic Bonding
• To obtain a noble gas configuration (a full valence shell), atoms may transfer electrons
from one atom to another.
• The atoms, now bearing opposite charges, attract each other, forming an ionic bond.

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Covalent Bonding

• Electrons are shared between the atoms to complete the octet .

• Molecules result from this covalent bonding.
• Valence electrons can be indicated by dots (electron-dot formula or Lewis structures) but this is
time-consuming.
• The usual way to indicate the two electrons in a bond is to use a line (one line = two electrons)
• When the electrons are shared evenly, the bond is said to be nonpolar covalent (H-H), or pure
covalent.
• Covalent bonds occur between atoms of similar electronegativity (close to each other in the
periodic table)
• When electrons are not shared evenly between the atoms, the resulting bond will be polar
covalent (H-F).

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 Pauling Electronegativity and Bond polarity
• Electronegativity is the ability of an atom to attract electrons in the covalent bond.
• It increases from left to right and from bottom to top in the periodic table.
• Electronegativities can be used to predict whether a bond will be polar and also predict the
direction of its dipole moment.
• Since the electronegativities of carbon and hydrogen are similar, C—H bonds are considered to be
nonpolar.
– Fluorine is the most electronegative atom and can stabilize excess electron density the best.
– A polar covalent bond has a slight positive charge on one end and a slight negative charge on the
other.

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 Dipole Moment (m) = d d

Dipole moment is defined to be the amount of charge separation ( d) multiplied by the bond length (m).
Charge separation is shown by an electrostatic potential map (EPM), where red indicates a partially
negative region and blue indicates a partially positive region.

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Lewis Structures

A Lewis structure is a very simple model of chemical bonding and the structure of molecules.

It only deals with valence shell e- \ the octet rule!

Procedure for obtaining good Lewis structures:

1) determine total number of valence shell e- (including ionic charge if present).
2) draw a skeleton of the molecule connected with single bonds.
3) determine number of remaining e-.
4) complete the octet of the terminal atoms.
5) left over e-? Place them on the central atom.
6) central atom short e-? Use lone pair e- from terminal atoms to create multiple
bonds.
7) determine the formal charges of all atoms. Formal Charges (FC): The formal
charge is the hypothetical charge on an atom in a molecule or ion.

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Nonbonding Electrons

• Also called lone pairs

• Nonbonding electrons are valence-shell electrons that are not shared between atoms.

Multiple Bonding

• Sharing two pairs of electrons is called a double bond.

• Sharing three pairs of electrons is called a triple bond.
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 Formal Charges (FC): The formal charge is the hypothetical charge on an atom in a molecule or ion.
Formal charges are a way of keeping track of electrons. They may or may not correspond to actual
charges in the molecule.
The best Lewis structures will have formal charges on the atoms that are zero or nearly zero.

formal charge = # valence e- - # assigned e-

OR = (# valence e-) – (# of bonds + # of unshared e-)
Example 1: Consider nitrosyl chloride, NOCl
Cl N O Cl N O Best Lewis
Cl 7 – [2+ 4] = +1 Cl 7 – [1 + 6] structure
N 5 – [3 + 2] = 0 =0
O 6 – [1 + 6] = -1 N 5 – [3 + 2]
: O: =0 +1
-1
Example 2: CH2O O Example 3: CO
6 – [2 + 4] : C O:
H C H
=0
What is the formal charge of the sulfur atom in the Lewis structure?

Draw Lewis structure indicating FC for: HCNH; NO+1

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Resonance Forms

• The structures of some compounds are not adequately represented by a single Lewis structure.
• We are only allowed to change the distribution of e -, i.e. the p bonds and lone pairs.
• atom positions do not change and All of the resonance structures must be proper Lewis
structures
• Resonance forms are Lewis structures that can be interconverted by moving electrons only.
• The true structure will be a hybrid between the contributing resonance forms.
• In a neutral molecule, the sum of the formal charges is zero. For an ion, the sum of the formal
charges is equal to the charge of the ion.

Resonance forms can be compared using the following criteria, beginning with the most important:
1. Has as many octets as possible
2. Has as many bonds as possible
3. Has the negative charge on the most electronegative atom
4. Has as little charge separation as possible
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Major and Minor Contributors

• The major contributor is the one in which all the atoms have a complete octet of electrons.

• When both resonance forms obey the octet rule, the major contributor is the one with the
negative charge on the most electronegative atom.

N 2O
-1
H2C NO2

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Non-Equivalent Resonance
• Opposite charges should be on adjacent atoms.
• The most stable one is the one with the smallest separation of oppositely charged
atoms.

Solved Problem: Draw the important resonance forms for [CH3OCH2]+. Indicate which
structure is the major and minor contributor or whether they would have the same
energy.

The first (minor) structure has a carbon atom with only six electrons around it. The
second (major) structure has octets on all atoms and an additional bond.

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Drawing molecules: Condensed Structural Formulas

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Line-Angle Drawings

• Sometimes called skeletal structure or stick figure.

• Bonds are represented by lines, and carbons are present where a line begins or ends and
where two lines meet.
• Hydrogens attached to carbon are not shown.
• Nitrogen, oxygen, and halides must be shown.
• Atoms other than carbon must be shown.
• Double and triple bonds must also be shown.

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Calculating Empirical Formulas

The following are items that need to be considered when calculating empirical formulas:
– Given % composition for each element, assume 100 g.
– Convert the grams of each element to moles.
– Divide by the smallest number of moles to get the ratio.
– The molecular formula may be a multiple of the empirical formula.

Your responsibility to find HOW.

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Arrhenius Acids and Bases
• Arrhenius acids are substances that dissociate in water to give H 3O+ ions.
• Stronger acids dissociate to a greater degree than weaker acids.

 Arrhenius bases are substances that dissociate in water to give hydroxide ions.
 Stronger bases (NaOH) dissociate more than weaker bases (Mg(OH) 2).

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Brønsted–Lowry Acids and Bases

Brønsted–Lowry acids are any species that donate a proton. Brønsted–Lowry bases are any species
that can accept a proton.

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Conjugate Acids and Bases
• Conjugate acid: When a base accepts a proton, it becomes an acid capable of returning that proton.
• Conjugate base: When an acid donates its proton, it becomes capable of accepting that proton
back.

Acid Strength

• an acid’s strength is expressed in its extent of ionization in water

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Base Strength

• The strength of an acid is inversely related to the strength of its conjugate base.

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Equilibrium Positions of Acid–Base Reactions

1. The acid–base equilibrium favors formation of the weaker acid and the weaker base.
2. The weaker acid has the larger pKa. The weaker base has the larger pKb.
3. The weaker acid and the weaker base are always on the same side of the equation. Both of them
are reactants, or both of them are products.

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Solvent Effects on Acidity and Basicity

• Water is amphoteric; it can react with an acid or a base.

• Its conjugate acid is the hydronium ion, and its conjugate base is the hydroxide ion.

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Effect of Electronegativity on pKa

• A more electronegative element

bears a negative charge more easily,
giving a more stable conjugate base
and a stronger acid.

Effect of Size on pKa

• The negative charge of an anion is more stable

if it is spread over a larger region of space.
• Within a column of the periodic table, acidity
increases down the column.

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Inductive Effects on Acidity

• Electron-withdrawing atoms and groups can stabilize a conjugate base through the sigma bonds
of the molecule.
• The magnitude of this inductive effect depends on the number of bonds between the
electronegative element and the site of the negative charge.

• Stronger electron-withdrawing groups stabilize the anion of the conjugate base.

• Multiple electron-withdrawing groups stabilize the conjugate base and increase the acidity.

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 Hybridization Effects on Acidity: The different hybridization states strongly influence
acidity.

Hybridization Effects on Acidity

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Effect of Resonance on pKa

• If the negative charge on an atom can be delocalized over two or more atoms, the acidity of
that compound will be greater than when the negative charge cannot be delocalized.
• The ethoxide anion is less acidic than the acetate ion simply because the acetate ion can
delocalize the negative charge.
• Methanesulfonic acid can delocalize the charge in three different resonance forms, making it
more acidic than the acetate ion.

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 Lewis Acids and Lewis Bases
• Lewis bases (called nucleophiles) are species with available electrons that can be donated to form a
new bond.
• Lewis acids are species that can accept these electrons to form new bonds. All M+n are lewis acids
• Since a Lewis acid accepts a pair of electrons, it is called an electrophile.

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