ORGANIC CHEMISTRY 307

Fall 2013
Lecture Notes I
Intro and Chapter 1
R. Boikess

Welcome to Chemistry 307, Organic Chemistry:

Be sure you understand the organizational and administrative aspects
of the course. Refer to the Sakai course site for the Syllabus, the Course
Information Document, and other documents that explain the use of the iclicker, the online instructional support (OWL, eBook) and Chem Draw.
How to Succeed in Organic Chemistry
1. The first few weeks are the key to success. So start immediately Learn
to understand and write [active skill] the different representations of organic
compounds [almost by reflex]. How? Practice
2. Develop a method for systematic memorization [flash cards or whatever
you are comfortable with]
3. Here is a recommended strategy. The lecture notes should be your first
point of attack. They tell you what is important and what approach we are
going to use. They wont always parallel your textbooks. Read them before
you read the textbooks. Then read the assignments in the textbooks before
the lectures, focusing on the things emphasized in the lecture notes. Come to
lectures, then reread the textbooks and the notes, do the homework, much of
which is on line, and do not look at the solutions in the solutions manual or
in CP until you have given it your all.
4. Make sure your knowledge is active; success depends on skills such as
drawing structures, assigning names, writing reaction mechanisms,
formulating synthetic routes, interpreting spectra, etc. Exams (check the
Sakai site for many exams from previous years) will have questions that
require hand written answers. Typical questions will start with Draw the
structures of or Give the names of or Write the mechanism of

or Propose a synthesis of . There will be a very small number of

multiple guess questions
5. Use recitations, review sessions, office hours, email etc to get help and
answers to your questions. We are committed to providing you as much help
as possible.
6. Before exams, solve the large number of practice problems that we will
send you, work out the exams from previous years, focus on and review the
material covered in the lecture notes.
Introduction
A. What is Organic Chemistry and why do we spend at least a whole year
studying it? Think about all the different substances you encounter every
day. Almost every single one is an organic substance.
1. Organic chemistry is defined as the chemistry of compounds of carbon,
[oversimplified all organic compounds contain carbon, but not all
compounds that contain carbon are organic.]To some extent definitions such
as these are arbitrary or historical. We shall use this one: Organic compounds
all have at least one C-H bond, except for a very few that have only a C-C
bond or a C-X bond(X conventionally means halogen). So compounds such
as sodium bicarbonate or calcium carbonate are not defined as organic
compounds.
Most (but not all) of the organic compounds we will consider in this
course consist of only nonmetals. There is, however, a large important
branch of organic called organometallic chemistry, in which the organic
compounds also contain at least one metal atom.
2. To some laypersons, organic chemistry has a different connotation,
related to organism or life. This connotation is mostly historical and comes
from the fact that virtually every chemical of life is organic, one reason why
Organic Chemistry is required for majors in the life sciences.
3. Historical: The Vital Force Theory, which postulated that any substance
from a living thing had a special, almost magical ingredient called Vital
Force, was abandoned in the 19th century. The first in a series of key
experiments that led to its abandonment was the preparation of urea from
apparent inorganic sources. This urea was indistinguishable from urea from
animals, as far as Wohler (who did the experiment) could tell. But the
difficulty of proving that something doesnt exist is the reason that it took

many more experiments and many years before everyone was convinced that
there was no magical, mysterious substance associated with living things.
4. Most known chemical compounds are organic. There are more than 72
million chemical substances known, most of them organic. That number is
increasing every day. (50 years ago there were fewer than 1 million, two
years ago there were 60 million). In addition there are over 64 million
genetic sequences known. Technically, each one is a different organic
compound.
B. Whats so special about Carbon? Why are there so many compounds of
Carbon? Review the material on the Periodic Table, the electronic
configurations of atoms, and covalent bond formation in your Gen Chem
book.
1. Position in the Periodic Table. In the middle of the second row, so its
small (can get close to other atoms and form multiple bonds) and in the
middle of the EN scale. Thus C is good at forming covalent bonds.
2. Has 4 valence electrons, so it can form 4 covalent bonds by electron
sharing with things that bring a total of 4 electrons. The 4 from C plus the 4
from things to which the C bonds result in a noble gas electronic
configuration around the C. When an atom in a compound is associated with
8 valence electrons we say that the atom has a completed octet.
3. The valence shell electron configuration is 2s22p2. You may have
learned about promotion in the past to explain the formation of four bonds
by C. It is an unnecessary and inaccurate complication. Just remember
carbon has 4 valence electrons and therefore forms 4 bonds, to complete its
octet. Any energy cost of changes in orbitals is more than offset by the
formation of bonds and octet completion. Remember bond formation is
energetically favorable.
Why are there so many compounds of carbon?
a. Carbon atoms can form chains. Most compounds of carbon contain
such chains, two or more carbon atoms linked together [One of the key
skills in organic chemistry is to be able to draw these chains and
understand how they are put together.]
b. We need to consider two issues, stability and reactivity, to explain
why so many compounds have these carbon chains.

c. Look at bond energies. The C-C (bond energy = 347 kJ/mol) is a

strong bond. That speaks to stability. The bond is strong because of good
orbital overlap, as we shall see.
d. But could C-C bonds form something better by chemical reaction
(reactivity)? The most common reagent on Earth is O2. But the C-O bond
energy is 358 kJ/mol, which is not very different from the C-C bond
energy. So C-C bonds are relatively unreactive under ordinary conditions.
e. We also observe that C-C bonds are not weakened when the C atoms
form chains or when other atoms are attached to the C atoms.
Review
A. Valence Shell Electronic Configurations
1. Shells and Subshells, Atomic Orbitals
a. Aufbau and electronic configuration
b. Valence shell is the key. In nonmetals it is the orbitals with highest
value of n.
2. Review electronic configurations of these important elements: C, H,
N, O, X (halogen), and (less important) P and S,). They are all nonmetals
and they are all found in organic compounds. Organic cpds with other
nonmetals are rare. Thus in this course we can focus on just a few
nonmetals, know their electronic configurations, electronegativities, and
other relevant atomic properties and not have to worry about a large
number of other elements.
B. Covalent Bonds
1. Electron pair sharing. When two atoms share one, two, or three pairs
of electrons we have a covalent bond.
2. The formation of covalent bonds is energetically favorable. This
very important principle operates under the conditions found on the
surface of our planet. (Note when we compare energies, lower energy
is better.) This principle has broad applications in Organic Chemistry.
There are a number of different ways that we can explain it depending
on how we choose to describe bonding.
One very simple explanation is based on electrostatics. The electron is
negative and the nucleus is positive. So there is a favorable interaction
between the electrons of an atom and its nucleus. If the atom now
shares its electron with another atom, the electron interacts favorably

with two nuclei. This advantage of electron sharing has limitations

based on distance and electron properties, however.
2. Nonmetals tend to form a preferred number of bonds: C = 4, H = 1,
N = 3 (and one lone pair), O = 2 (and two lone pairs), X = 1(and 3 lone
pairs). Also, when they are in their lowest oxidation states P = 3, (like
N), S =2 (like O) when they combine with other elements. As we shall
see, some of these nonmetals can form other numbers of bonds in some
chemical species. When an atom does not form the preferred number of
bonds, it will have a charge, not only if it is part of an ion, but even in a
neutral compound. We refer to such a charge as a formal charge.
3. Maximum number of bonds: [very important Second Row Elements
do not expand Octets under ordinary conditions] For H = 1, C = 4,
and F = 1, the preferred number is also the maximum. But the other
elements can form more bonds than the preferred number: N = 4 (formal
or ionic charge +1), O = 3 (formal or ionic charge +1), X (Cl, Br, I) in the
1 oxidation state = 2 (formal or ionic charge +1). Note that when X is
bonded to O, X will be in a higher oxidation state this rule does not
apply. The maximum number of bonds for P = 5 and for S = 6 because
they are 3rd row elements and can expand octets using d-orbitals. When
they do so they are in higher oxidation states and bonded to more
electronegative elements, such as X or O. When P and S are in their
lowest oxidations states (-3 and -2 respectively) they behave like N and
O, respectively.
4. Descriptions of Bonding. Since chemical change is the making and
breaking of bonds and since the properties of a substance are closely
related to its bonding, it is very important for us to have useful and easy
ways to describe the chemical bonds in a substance. As we shall see,
there are a number of different ways to describe bonds. We choose the
description that is most convenient for us, or that best explains whatever
property is of interest to us.
The Localized Bonding Model is the simplest and most familiar. The
focus is on the valence shell electron pairs associated with each atom of
the chemical species. We draw Lewis structures, which tell us what is
attached to what and how, and which provide an accounting of the
valence shell electrons. Being able to draw Lewis structures is a vital
skill for Organic Chemistry. Use the available material (CP 1.1-1.2, BF
5

1.2A-C) and problems in both books to make sure you master this skill as
soon as possible. If you dont get very good at drawing Lewis structures
very soon, you will not succeed in 307.
We will use lines (not pairs of dots) to represent shared pairs and dots if
necessary to represent lone pairs. We will often be permitted to write
simplified Lewis structures, in which we do not show all the lone pairs
and in which we do not show some bonds of less interest such as some
bonds to H.
5. Resonance (CP 1.3, BF1.8 ).
a. When you can draw more than one Lewis structure with the same
skeleton structure (what is attached to what) for a species, the actual
compound (or species) is a blend of all the Lewis structures that can be
drawn. But the structures must be reasonable (not appear too silly or
unusual) with completed octets (if possible) and preferred numbers of
bonds, thus minimizing formal charges. (The idea that the most
reasonable structures are those with the minimum possible formal
charges is called the Principle of Electroneutrality.)The more reasonable
the structures, the more they contribute to the description of the actual
structure. There is a discussion in CP1.3 of what makes a given structure
more or less reasonable. Be sure you understand it. The most important
factor is the number of bonds. The more bonds the better. Two equivalent
reasonable structures are best. When we can draw different reasonable
Lewis structures with the same skeleton structure for a given compound,
these structures are called contributing structures and they are
imaginary. The real structure of a compound that cannot be described by
a single Lewis structure is a blend of the contributing structures.
Remember, contributing structures do not correspond to anything real.
They are simply imaginary drawings we have chosen to use to represent
the structure of a real substance.
Consider the following two structures for the acetate ion. (They are
drawn without showing the C-H bonds, but are still perfectly clear.)
Remember that we move only the electrons and the lone pairs, not the
atoms, in order to draw the different structures. In other words, what is
attached to what doesnt change.

Note the two curved red arrows in the figure. These kinds of
arrows are used by organic chemists to do electron bookkeeping. We will
use such arrows throughout the year to account for real or imaginary (as
in this case) movement of electrons. Being able to use these arrows
correctly is an essential skill you must have. The tail of the arrow points
to an electron pair in a given location in a structure. The head of the
arrow points to its new location. The double barb of the arrow indicates
that we are referring to a pair of electrons. If we wanted to show the
movement of a single electron we could use an arrow with a single barb.
We will use these arrows not only to generate contributing structures as
shown here, but especially to explain how reactions take place, what is
called a reaction mechanism.
Here the movement of the electron pairs is imaginary because a
contributing structure is imaginary. But using these arrows helps us to
write the various important contributing structures of a species, given one
of them. As you can see, only lone pairs or electrons in pi bonds can
undergo this movement in contributing structures. Practice drawing these
arrows to generate additional contributing structures, from one that you
are given. Being able to draw and use these arrows for contributing
structures and reaction mechanisms is an essential skill. Here is
another example

Notice that these two contributing structures are not identical, but they
are both reasonable. Which one is more important and why?
6. Formal charges (which are sometimes also ionic charges) can be
related to the number of bonds, in the context of completed, but not
expanded octets. Its all electron bookkeeping.
The table below shows the relation between number of bonds and
formal charge for elements with completed octets and no octet
expansion. Learn and understand this table. It will be very useful. Do not
use the complex formula that was used in Gen Chem and is in Section
1.2D of BF, unless octets are not complete. (Later on we will consider
species in which an element does not have a completed octet). Just learn
this table, which is not difficult once you see the overall logic.
Element

Preferred
# of bonds
4
1
3

Maximum # Formal Fewer #

of bonds
Charge of bonds
C
4
3
H
1
no
N and P*
4
+1
2
1
O and S* 2
3
+1
1
F
1
1
no
Cl, Br, I* 1
2
+1
no
* In their lowest oxidation states.

Formal
Charge
-1
-1
-2
-1

C. Representations of Compounds and their Structures Very Important

What do we want to show? Increasing levels of information about
molecular structure, but we need shorthand to keep things manageable. The
shorthand is based on the fact that H always forms just one bond and the
8

other common atoms in neutral organic molecules generally have a fixed

number of bonds. (C = 4, N = 3, O = 2, and X (halogen) = 1) and have
completed octets. These rules tell us what is attached to what in our
shorthand structures.

Consider acetic acid.

a. composition: C2H4O2 is not a very useful formula in Orgo because of
isomerism. (Define). There are at least 8 different structures (without formal
charges) that can be drawn with this composition. (See how many you can
draw)
b. Lewis Structure based on preferred number of bonds showing all the
valence shell electrons, bonding pairs as dashes and lone pairs as dots

is tedious, but tells us what is attached to what and how. Often, as here, we
need some information about the compound to draw the Lewis Structure. In
this case the information is that it is an acid (actually, as we shall see, a
carboxylic acid), which tells us that there is an O-H attached a C=O.
c. Leave out the dots but leave in the dashes. We can add to 8. But be
careful. If you decide to include the dots on a given atom, you must include
all of them. So, for example, the structure

for water is wrong. It

must be
if you need to include dots. Structures without the dots are
sometimes called Kekul structures. Note that we have also omitted the CH bonds here.
O
C
H 3C

OH

d. Leave out all the dashes. We can add to 4, 2, or 1 (You must be able to
do this automatically) or accommodate for formal charges. We can write
CH3CO2H and because we know the preferred number of bonds for the
atoms, we can work out the structure. Note the difference with the formula
in Part a. While we can work out the structure of a simple molecule such as
acetic acid from this kind of condensed formula, it will not be so easy for
more complex compounds. It is for that reason that we tend to leave out the
dashes only for bonds to H and for carbon carbon and some other single
bonds. Otherwise we usually include the other kinds of bonds, unless there is
no ambiguity. This approach leaves room for judgment. So its usually okay
to include extra information. You must be careful not to leave out so much
that there is ambiguity.
e. We can do even more condensation, consistent with unambiguity:
CH3CH3 (or even C2H6), CH3CH2CH3, (or C3H8) or CH3CH2CH2CH3 (but not
C4H10, why?). Answer: There are two compounds with this formula. It could
also be CH3CH(CH3)CH3, a condensed representation of

Note: You must practice until you can write and understand
these kinds of condensed structures, reflexively and effortlessly.
f. There are some conventions we tend to follow in drawing these
condensed structures. The main (more later) carbon chain is written
horizontally with the associated hydrogens generally to the right of each
carbon or if they are attached to other atoms such as N or O, to the right of
them as well. Other substituents in the middle of the main chain are
indicated with vertical lines or parentheses. It is essential that a condensed
structure corresponds to only one correct molecule and can be easily
understood.
g. The point of the condensed structures is to save space. So we can go
even further when things are unambiguous. Examples: CH3(CH2)5CH3 or
(CH3)4C.
h. Once we are comfortable adding up to 4, we can condense even further.
In a line-angle formula we do not show C and H atoms or even C-H bonds.
A line is a C-C bond with the C at each end assumed to have the correct
number of Hs attached.

10

______

This simple line represents ethane, C2H6. When two lines meet, there is
only one C atom at the connection, as in propane (C3H8)
A zig zag line is a chain of C atoms and the ends are CH3 groups. So the
molecule CH3(CH2)3CH3 can be written as
This method of drawing structures is the one we shall use most often
because this is the way our software (Chem Draw) does it. There are
directions on the Sakai course page for downloading this software. It is an
excellent learning tool that can provide you help in a number of areas of the
course. (and its free).
There is also a document on the web site called Drawing Structures that
you will find very helpful.
f. Geometry and 3-D. In 2-D we use projection or perspective drawings to
give 3-D information. The simplest projection is the dashed (or dotted) linewedge projection. We draw bonds in 3 ways. If the bond is in the plane of
the paper it is an ordinary line, in back it is a dashed line, and in front it is a
wedge. We draw the main carbon chain in the plane of the paper. We will
learn other kinds of projections later that work well for specific situations.
Below is a projection for ethane,

g. In 3-D use a model. (Learn to use the model kit that came with your
textbook.)
D. Orbital Descriptions of Bonding
While the localized bonding model and the condensed structures we
develop from it are very useful in conveying information about what is
11

attached to what in molecules, it is of limited use in helping us

understand and predict the properties and chemical behavior of most
substances. More refined and useful descriptions are based on
combinations of the atomic orbitals of the valence shell of the atoms.
1. Please review thoroughly and be certain you understand the
coverage of orbitals in Gen Chem.
Very briefly, because of the wave nature of the electron, we cant
pinpoint its exact location. Instead we describe it by designating a region
of space around the atom in which there is a high probability of finding
the electron. In order to represent conveniently this region of space by a
picture, we enclose it inside a surface of constant probability (a set of
points at all of which there is an equal probability of finding the
electron). The surface is made big enough so it encloses 90% of the
probability of finding the electron. Remember if you could look at an
atom or molecule, you would not see an orbital. It is just a picture we
draw to describe a region of space where an electron may be found.
You can think of the electron in a region of space as a standing wave,
which is a wave that vibrates, up and down or side to side, in place like a
guitar string; but does not propagate like an ocean wave or a light wave.
It can be described by a mathematical function called a wave function.
The wave function, like other mathematical functions has a sign (+ or -).
Do not confuse this sign with an electrical or arithmetical sign.

Within the enclosed region of space, the probability of finding the

electron is not the same at every point. There are actually points, called
nodes, where the probability is zero. Notice that the wave has crests ( +
sign of the wave function) and troughs (- sign of the wave function)
Within the enclosed region of space the sign of the wave function may
or may not be the same throughout. As we shall see this characteristic of
some orbitals can have an important influence on bonding.

12

2. In order to describe bonding on the basis of combinations of atomic

orbitals, we should understand some of the features of orbitals. Again,
this material was presented in Gen Chem and you should review it.
Of special interest to us are the energies and sizes of orbitals, which are
given mainly by the n quantum number; the shapes of orbitals, which are
given by the l quantum number; and the sign of the wave function in
different regions of orbitals.
We need consider only a small number of orbitals in Organic
Chemistry, because we encounter so few elements. Most of these are in
the second row, so we need to focus mainly on the 2s and the 2p orbitals.
Hydrogen has only a 1s orbital. We will never be concerned with d
orbitals (in this course) and rarely with 3s and 3p orbitals (only in P, S,
and Cl)
An s orbital is represented as a sphere, whose size increases with an
increase in n the principal quantum number. The sign of the wave
function is the same everywhere, as shown by the single red color. It
could also have been a single blue color.

A p orbital has two lobes with a nodal plane at the nucleus. The wave
function has a different sign in each of the two lobes, as shown by the red
color in one lobe and the blue color in the other. Similarly its size
increases as n increases.

3. Combinations of Atomic Orbitals

13

There are two types of orbital combinations.

a. Orbitals on different atoms can combine to form molecular
orbitals, which can be the basis for the formation of bonds.
A bond is described by describing the atomic orbital on each
atom and how the two combine.
b. Atomic orbitals on the same atom can combine to form
different types of atomic orbitals that are especially useful
for forming bonds with other atoms. These orbitals are
called hybrid orbitals.
c. There are certain rules that have to be followed when
orbitals are combined. Do not be misled by the word
combine, which has a somewhat different meaning here
than in the macroscopic world. These rules are very
important and have a profound effect on our descriptions of
bonding.
i.

The number of orbitals is the same before and after

combination. For example, if two orbitals
combine, two new orbitals are formed. This rule
can be called conservation of the number of
orbitals.

ii.

The total energy of the orbitals is the same before

and after combination. Thus the total energy of the
two orbitals before they combine is equal to the
total energy of the two orbitals formed by
combination. This rule can be called conservation
of energy.

iii.

The energy and nature of an orbital formed by

combination of two other orbitals can depend in a
major way on the signs of the wave functions in
the combining orbitals and how they come
together.

4. Molecular Orbitals
Lets look first at the formation of molecular orbitals by combination
(or overlap) of two atomic orbitals, each on a different atom.
a. If two atomic orbitals overlap, two molecular orbitals are formed.
One (the good one) is of lower energy than either of the atomic

14

orbitals and therefore the other one must be of higher energy. The
decrease in energy is exactly offset by the increase in energy. The
lower energy orbital (which can hold two electrons) is called the
bonding molecular orbital and it is where the pair of electrons that
forms the bond is found. The orbital of higher energy is called the
antibonding orbital and is not normally used. (If it has to be used,
the result is destabilization). These relationships are summarized
below for the overlap of two 1s orbitals to form H2.

Note that combination of two wave functions with the same sign
(constructive interference) produces the bonding orbital and combination
of those with opposite signs (destructive interference) produces the
antibonding orbital. We can understand what a bonding orbital represents.
It is a picture of the region of space where the shared pair of electrons is
most likely to be. The pair is most likely to be there because the energy
associated with that region of space is low.
An antibonding orbital is a little harder to understand. It is a picture
(not a thing) of another region of space where electrons are allowed to be.
But when an electron is in that region of space it has a relatively high
energy. So as long as the bonding orbital is available thats where the
electrons go. But an orbital can only hold two electrons, so any additional
electron must be in the high energy antibonding orbital, which leads to
15

destabilization. The antibonding orbital (region of space) also comes into

play when a molecule absorbs energy. Recall from Gen Chem that when
energy is absorbed by a species an electron jumps from a relatively low
energy orbital to a higher energy orbital, such as the antibonding orbital.
b. We use two basic pictures to describe how atomic orbitals can
combine (or overlap) to form a bond.
One is called sigma () overlap, which was shown above for
H2. The orbitals overlap along the internuclear line. This kind of
overlap is the only one possible with an s orbital and can also
occur with p orbitals. The bond formed in this way is called a
sigma bond. There can only be one sigma bond between two given
atoms.
The other is called pi () overlap and it can take place between
two parallel p orbitals. The bond formed in this way is called a pi
bond. Because there is a sign change in wave function between the
two lobes of a p orbital we have to be careful to match the signs.
Two atoms can form one or two pi bonds between them in addition
to the sigma bond. So we describe a double bond as one bond
and one bond and a triple bond as one bond and two bonds
between the two atoms that are bonded.

Common sense and experience correctly predict that bonds

are generally stronger than bonds because the overlap is better.
16

There is another consequence of the different geometrical

requirements for and overlap. When two atoms (with their
other attached atoms) are connected by a bond, rotation around
the bond does not affect the overlap. We describe this situation as
free rotation and it exists for single bonds. On the other hand,
rotation around a bond does change the nature of the overlap and
therefore weakens the bond. Since weakening bonds is
disadvantageous such rotation generally does not occur near room
temperature. We say there is restricted rotation around multiple
bonds (which consist of at least one bond).
5, Hybrid Orbitals. Review this Gen Chem material very thoroughly. It
will be critical in this course.
Two or more orbitals on the same atom can be combined to
form hybrid orbitals. Hybrid orbitals provide a better description of the
bonds that the atom forms than a description based just on atomic
orbitals.
Remember the two important rules that apply to combinations of
atomic orbitals: conservation of the number of orbitals and conservation
of energy.
Suppose we combine a 2s orbital and a 2p orbital that are on the same
atom. We form two new orbitals, each of which is one part s and one part
p. We call these two new orbitals 2sp hybrid orbitals. Their energy is the
average of the energy of the 2s and the 2p that combined to form them.
Still remaining on the atom are two unhybridized 2p orbitals. What is the
advantage of hybridization? The hybrid orbital is more directional than
either an s orbital (not directional at all; it is a sphere) or a p orbital,
which points equally in two directions. These hybrid orbitals are very
good for bond formation, which are directional bonds along the
internuclear line. We can use the remaining unhybridized 2p orbitals to
make bonds if necessary
Continuing the same reasoning, we can combine a 2s orbital and two 2p
orbitals to make three hybrid orbitals, each of which is one part s and two
parts p. We call it a 2sp2 orbital. We use exponents to indicate the
composition of the orbital. Read it as 2s1p2, but write it as sp2. Still
remaining is one unhybridized 2p orbital, which could be used for a
bond, if necessary.

17

Finally we can combine all four orbitals in the n=2 valence shell to
make four hybrid orbitals each of which is one part s and three parts p.
Using the same notation these four orbitals are 2sp3. (2s1p3).
How do we use hybridization to describe the bonding in a molecule?
i. Look at each atom in the molecule, one by one and
determine whether or not it is hybridized. In order for it to
be hybridized it should be part of at least two sigma bonds,
that is it should be bonded to at least two other atoms.
Terminal atoms need not hybridized. Thus H and F are never
hybridized and the other halogens are never hybridized
when bonded to carbon. While it is better not to hybridize
terminal O atoms, as in a C=O bond or terminal N atoms as
in a
bond, BF does hybridize these atoms. Either
way is okay, but in this course we shall opt for unhybridized.
ii. Assign a hybridization by counting the number of sigma
bonds and lone pairs. If there are two sigma bonds and no
lone pairs the atom is sp hybridized. It the total of sigma
bonds and lone pairs is three (2 sigma bonds and one lone
pair or 3 sigma bonds), the atom is sp2 hybridized. If the
total of sigma bonds and lone pairs is four (2 sigma bonds
and 2 pairs or 3 sigma bonds and 1 pair or 4 sigma bonds),
the atom is sp3 hybridized.
iii. Once you assign a hybridization to an atom, you know what
hybrid orbitals it uses to form sigma bonds and hold its lone
pairs. (Remember, when the atom is hybridized, the lone
pairs are in hybrid orbitals.)
iv. Because there is a very close connection between
hybridization and bond angles, you are also able to predict
the geometry of a molecule from its hybridization.
6. Properties of Covalent Bonds Lets look at and apply some of the
attributes of covalent bonds presented in Gen Chem that help us describe
molecules and understand their behavior.
a. The strength of a bond can be expressed as its bond energy: the heat
(enthalpy) required to break the bond back to the atoms in the gas phase.
What makes a strong bond? Good overlap, multiple bonds better, (although
double is usually not twice single, why?), other factors to be discussed. The
stronger the bond, the more energy it takes to break it and the more energy is
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released when it forms. Molecules with only strong sigma bonds are
generally relatively stable and often relatively unreactive.
b. Think of bonds as lines connecting the centers of the two atoms attached
to each other to understand some other properties.
c. Bond length. Indicates how good overlap is. Shorter bonds tend to be
better, but limited by not getting the atoms so close that the nuclei repel each
other. Thus smaller atoms tend to form stronger bonds [average bond
energies: C-H 413 kJ/mol, C-C 347 kJ/mol] but other factors also operate.
d. Bond angles VSEPR and hybridization must be consistent. We describe
hybridization and bond angles (and thus molecular geometry) based on an
ideal geometry. Most substances do not have an ideal geometry, but many
are close. The ideals are based on the hybridization of an atom. Tetrahedral
geometry (bond angles of 109.5) is the ideal for sp3; trigonal planar
geometry (bond angles of 120) is the ideal for sp2, and linear geometry
(bond angles of 180) is the ideal for sp. We can then predict the deviation
from the ideal by a VSEPR approach in which lone pairs and multiple bonds
are thought of as bigger (and therefore more repulsive to other electrons)
than single sigma bonds. Different EN can also be a factor in causing
deviations from ideal, as we shall see.
e. Bond moments; unequal sharing due to EN, (mostly). All the nonmetals
except H are more EN than C. Review polarity related to chemical behavior
from Gen Chem. Also review dipole moments and vector addition of bond
moments, which have magnitude and direction.
f. Lets apply some of these ideas to an actual molecule, chloromethane:
CH3Cl.
i. Connectivity comes from preferred number of bonds. Draw the one
that looks the best. Use the Electroneutrality principle, which says that
absent other information, the best structure is the one with the least
formal charge. There are really no other sensible choices here, but that
will not always be the case.

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ii. Hybridization comes from 4 bonds around C. Geometry is

tetrahedral. Discuss which orbitals overlap and do not hybridize Cl. (1s
of H or a 3p of Cl with the 2sp3 orbitals of C)
iii Methane has ideal tetrahedral geometry,

but CH3Cl does not because of differences between Cl and H.

iv Bond Length: C-Cl 178 pm. C-H 111 pm. Cl is more EN than H.
Where are the electrons? Predict and explain the bond angles: answer: HC-Cl 108.0 and H-C-H 110.9. Two rationales. The electronegative Cl
uses a hybrid orbital with more p character, because these electrons are
not so tightly held by the C. More p character means a smaller bond
angle (sp3 is 75% p, bond angle 109 and sp2 is 67 % p, bond angle 120).
Or VSEPR the pair in C-Cl bond is further from the C allowing the other
angles to spread.

v. Dipole moment is 1.86 D compared to C-Cl bond moment, which is

1.56 D because of the EN difference. The C-H bond moment is small,
0.30 D, and in the direction of the C. Shown as vectors. When three
vectors of equal magnitude are directed toward or from the corners of a
regular tetrahedron their vector sum is a vector equal in magnitude to one
of the three and directed to or from the fourth corner of the tetrahedron.
So the result of the three C-H vectors is a vector of magnitude 0.3
pointing toward the Cl. Which is then added to the C-Cl vector.

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vi Bond Strength: C-Cl=350 kJ/mol compared to C-F=451 kJ/mol and

C-Br=294 kJ/mol. Two factors influence bond strength, size and EN.
Small size and large EN difference tend to make bonds stronger. We
predict that C-H should be stronger than C-C because of size. It is by
more than 40 kJ/mol and C-O should be stronger than C-N because of
EN. It is by over 50 kJ/mol
g. Lets do another, C2H4, systematic name ethene, but in common
usage [discuss] ethylene.
i. Connectivity comes from preferred number of bonds.

ii. Hybridization comes from 3 bonds and no lone pairs around C.

Geometry is trigonal planar. Discuss what we see and what the sigma-pi
description really is.

iii We predict the double bond is stronger, shorter, and bigger.

Measurements indicate that it is.
iv We predict that the geometry is not quite ideal because there are two
types of bonds and two types of atoms.

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v The measured bond angles are indeed not ideal. HCH = 118 and
HCC = 121.7

These bond angles can be explained in several ways. The simplest

explanation is that the double bond is bigger than a single bond and
therefore repels nearby electrons (in this case in the C-H bonds) more.
7. One of the major challenges of Organic Chemistry is to find a way to
organize and systematize an enormous amount of information. The most
common approach to this problem is to classify compounds based on
their composition and certain structural features and then to focus on the
properties of the structural features, which are to a large extent
independent of the specific compound. This approach is introduced in
Section 1.3 of BF. You should learn the material in this sections now. It
will make things easier for you as we go along.
Virtually all organic molecules have carbon-carbon single bonds and
carbon-hydrogen bonds. These parts of the molecule have very little
effect on chemical behavior. Most organic molecules have one or more
additional structural features such as multiple bonds or other elements
(mostly commonly O or N or X). Any part of the molecule that is
something other than a C bonded to other Cs by single bonds and to Hs
is called a functional group. The chemical behavior and to some extent
the physical behavior of the molecule is determined primarily (but not
entirely) by the functional groups. Most chemical change takes place at
the functional groups. So we are going to focus on functional groups,
their chemistry, their interconversions, their preparation, and their
properties in general. The overall organization of the material in the
course will be based primarily on functional groups. BF mentions the
important ones and you should learn them.

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