314 Topic 01 Pages 27-64

Chapter 1 Benzene Blues 27
The Hybridization Model of Atoms in Molecules
An important question facing chemists about 80 years ago, was, “How does one go from recently
invented atomic orbitals to rationalizing the three common shapes continually found in organic chemistry
and biochemistry (tetrahedral, trigonal planar and linear)?” Linus Pauling, a two time Nobel prize winner
(for chemistry and peace), was the chemist who figured out how to make the mathematics of quantum
mechanics into qualitative pictures that organic chemists could understand in the 1930s. His approach
was so simple and so good that we are still using it today, even though there are more modern alternative
ways of explaining organic shapes. Thank you Linus!
The following molecules provide examples of all three basic shapes found in organic chemistry.
In these drawings a simple line indicates a bond in the plane of the paper, a wedged line indicates a bond
coming out in front of the page and a dashed line indicates a bond projecting behind the page. You will
have to become at least a mediocre artist to survive in organic chemistry.
H H
H
H H H H
C C C C H C C H Ca Cb Ca
H H H H
H H H
allene
ethane ethene ethyne trigonal planar carbon atoms
tetrahedral carbon atoms trigonal planar carbon atoms linear carbon atoms at the ends and a linear
carbon atom in the middle
HCH bond angles ≈ 109o HCH bond angles ≈ 120o (116o) HCC bond angles = 180o
HCC bond angles ≈ 109o CCH bond angles ≈ 120o (122o) HCaH bond angles ≈ 120o
HCaCb bond angles ≈ 120o
CaCbCa bond angles = 180o
Our current task is to understand hybridization. Even though you probably already studied
hybridization, this topic is way too important to assume you know it from a previous course. Hybrids are
new creations, resulting from mixtures of more than one thing. Our mixtures will be simple combinations
of the valence electrons in the 2s and 2p orbitals on a single carbon atom. Though not exactly applicable
in the same way for nitrogen, oxygen and the halogens, this model will work fine for our purposes in
beginning organic chemistry. We will mix these orbitals three ways to generate the three common shapes
of organic chemistry: linear (2s+2p), trigonal planar (2s+2p+2p) and tetrahedral (2s+2p+2p+2p).
We will first show how the three shapes can be generated from the atomic orbitals, and then we
will survey a number of organic structures, using both two-dimensional and three dimensional drawings
to give you abundant practice in using these shapes. You should be able to easily manipulate these
shapes, using only your imagination and, perhaps, pencil and paper, if a structure is a little more
complicated. If you have molecular models, now is a good time to get them out and assemble them
whenever you are having a problem visualizing or drawing a structure. Your hands and your eyes will
train your mind to see and draw what you are trying to understand and explain.
Organic chemistry and biochemistry are three dimensional subjects. Just like you don’t look at
every letter in a word while you are reading, you can’t afford to struggle with the shape of every atom
while examining a structure. If you are struggling to comprehend “shapes”, you will never be able to
understand more complicated concepts such as conformations, stereochemistry or resonance as stand
alone topics, or as tools for understanding reaction mechanisms. You have to practice (correct your
errors), practice (correct your errors), practice (correct your errors) until this skill is second nature, and
the pictures and terminology are instantly comprehended when you see a structure…and you have to do it
quickly, because there’s a lot more material still to be covered. However, anyone reading these words can
do this – and that includes you!
Carbon as our first example of hybridization
1. sp hybridization – carbon and other atoms of organic chemistry
Our first example of hybridization is the easiest and merely mixes a 2s and a 2p atomic orbital to
form two sp hybrid orbitals. Remember that when we mix atomic orbitals together, we create the same
number of new “mixture” orbitals. This is true for molecular orbitals on multiple atoms, as shown just
above (σ, σ*, π and π*), and for hybrid orbitals on a single atom, as shown below (sp, sp2 and sp3). We
might expect that our newly created hybrid orbitals will have features of the orbitals from which they are
created…and that’s true. The 2s orbital has no spatially distinct features, other than it fills up all three
dimensions in a spherical way. A 2p orbital, on the other hand, is very directional. Its two oppositely
phased lobes lie along a single axis, in a liner manner. Newly created sp hybrid orbitals will also lay
along a straight line in a linear fashion, with oppositely phased lobes, because of the 2p orbital’s
contribution. The two new sp hybrid orbitals point in opposite directions, having 180o bond angles about
the sp hybridized atom.
The scheme below shows a hypothetical process to change an isolated “atomic” carbon atom into
an sp hybridized carbon atom having four unpaired electrons, ready for bonding. The vertical scale in the
diagram indicates potential energy changes as electrons move farther from the nucleus. Unpairing the 2s
electrons allows carbon to make two additional bonds and acquire the neon Noble gas configuration by
sharing with four other electrons. There is an energy cost to promote one of the 2s electrons to a 2p
orbital, but this is partially compensated by decreased electron/electron repulsion when one of the paired
electrons moves to an empty orbital. The really big advantage, however, is that two additional highly
directional sigma bonds can form, each lowering the energy of the carbon atom by a considerable amount
(lower potential energy is more stable). The combination of all the energy changes is quite favorable for
carbon atoms, whether sp, sp2 or sp3 hybridized. It’s important that you understand the qualitative ideas
presented here with two orbitals (2s + 2p), because we are going to do it all over again with three orbitals
(2s + 2p + 2p = three sp2 hybrid orbitals) and four orbitals (2s + 2p + 2p + 2p = four sp3 hybrid orbitals).
mix (2s and 2p), two

promote a 2s ways (2s + 2p) and
2p's electron to a 2p's (2s - 2p) to create two 2p 2p
2p orbital sp hybrid orbitals
sp sp
2s 2s
sp arrangement for carbon
isolated carbon atom atom bonded to other atoms,
(not typicalin our world) two p orbitals remain to
become part of pi bonds
higher,
less stable cost = promotion energy ≈ 100 kcal/mole
Overall, this would gain = electron/electron repulsion in s ortibal is removed ≈ 20-40 kcal/mole
potential be a favorable trade. gain = two additional bonds are possible ≈ 150-200 kcal/mole
energy gain = more directional orbitals form, that have better overlap of electron
density between the bonding atoms, thus forming stronger bonds
lower,
more stable
The energy diagram shows that 2s electrons are held more tightly than 2p electrons (because they
are closer to the nucleus, on average). Because sp electrons have 50% s orbital contribution, they are also
held more tightly than 2p electrons [2s (100% s) > sp (50% s) > sp2 (33% s) > sp3 (25% s) > 2p (0% s)].
The greater the percent 2s contribution in a hybrid orbital, the more tightly the electrons are held by the
atom. In a sense, this is a property similar to electronegativity, except that changes occur within the same
kind of atom, based on hybridization, instead of in different types of atoms based on Zeffective or distance
from the nucleus. This idea will be developed more fully in our acid/base topic.
Creating the hybrid orbitals
We can show the orbital mixing to create sp hybrid orbitals pictorially by using images of 2s and
2p orbitals. We simplistically represent the mathematics of the mixing by showing addition of the two
orbitals and subtraction of the two orbitals. This is close to what happens, but not exactly correct. It does
serve our purpose of symbolically changing the phase of the 2p orbital in the subtraction, generating the
second sp hybrid orbital pointing 180o in the opposite direction from the first sp hybrid orbital. Phase is
important here and adds constructively when it is the same (bonding) and destructively when it is
opposite (antibonding). This will produce a larger lobe on the bonding side of the sp hybrid orbital (more
electron density to hold the atoms together) and a smaller lobe on the antibonding side of the sp orbital
(less electron density). Greater electron density between the bonded atoms will produce a stronger bond.
The 2s and 2p orbitals are artificially separated in the first part of the scheme for easier viewing.
Even though the orbitals are drawn separately, remember that the center of the carbon atom is at the
middle of the 2s orbital and at the node of all of the hybrid and p orbitals.
superimpose
orbitals (2s + 2p)
C C C C
2s add 2p spa
2s + 2p
The nucleus
The nucleus of the carbon
of the carbon atom is here.
atom is here.
superimpose
orbitals (2s - 2p)
C C C C
spb
2s subtract 2p (reverses phase)
2s - 2p
The Complete Picture of an sp Hybridized Carbon Atom

An isolated sp hybridized carbon atom for viewing. This represents the spa hybrid orbital. The
A bonded carbon atom would need orbital overlap small, opposite phase lobe on the backside
for each orbital present, spa, spb, 2pz and 2px. 2pz has been left off to simplify the picture.
Carbon has one electron

spb C available for each orbital
spa
to share with bonding
partners.
2px
This represents the spb hybrid orbital. The
small, opposite phase lobe on the backside There remain two 2p orbitals which are perpendicular
to the two sp hybrid orbitals and to each other. Each
has been left off to simplify the picture. 2p orbital extends along its entire axis with opposite
phase in each lobe.
Two sp carbon atoms bonded in a molecule of ethyne (…its common name is acetylene)
The simplest possible way to place our sp hybridized carbon into a neutral molecule is to bring
another sp hybridized carbon up to bond with three of its atomic orbitals: one sp hybrid sigma bond, along
the bonding axis of the two carbon atoms and two pi bonds. One of the pi bonds will lie above and below
the sigma bonded carbon atoms in the plain of the page. The other pi bond will lie in front and in back of
the carbon atoms, perpendicular to the plane of the page. On the other side of each carbon atom, 180o
away from the other carbon atom, we can attach a simple hydrogen atom, using its 1s atomic orbital to
overlap in a sigma bond along the bonding axis (a first bond is always sigma bond).
C C H C H
C
σCC
σCH σCH
C C C C
Ethyne has five total bonds: three

sigma bonds and two pi bonds.
πCC πCC
top and bottom front and back
The shape of each sp carbon atom is linear and allows the electrons in the σ bonds and the atoms
they are bonded to, to be as far apart in space as possible, minimizing the electron/electron repulsion. The
small backside lobe of each sp orbital has been omitted for clarity, since the bond on the side of the large
lobe has the bulk of the electron density and determines where the bonded atom will be.
In organic chemistry sigma bonds (σ) are always the first bond between two atoms, resulting from
overlap along the bonding axis (of hybrid orbitals), while pi bonds (π) are second and third bonds
resulting from the overlap of p orbitals, above and below (or in front and back of) the bonding axis. (I’m
repeating myself on purpose.)
Our molecule of ethyne now looks as shown, including all of the lobes of the orbitals (except for
the small backside lobes of the hybrid orbitals). However, it looks a little too congested with details to
see everything clearly, and it’s way too much work to draw routinely. If we tried to add other non-
hydrogen atoms, it would get too messy as well.
These terms all go together. For neutral sp carbon,

knowing any one of them, implies all of the others.
sp hybridized carbon
carbon atom shape = linear
H C C H bond angles about sp carbon = 180o
number of sigma bonds = 2
number of pi bonds = 2
We rarely draw our 3D structures like this, preferring simpler ways of representing the details. In
my early years of teaching, my preference was to draw single lines for the sigma bonds (simple lines in
the plain of the paper, wedged lines in front of the paper and dashed lines in back of the paper), and to
include the lobes of the p orbitals with a line connecting the lobes on both sides to show the nature of the
pi bonding. However, over the years the students have convinced me that it is easier for them to see the
details if the p orbitals are also drawn as straight lines (same 3D conventions: simple, wedged and dashed
lines). Connecting lines are still drawn on both sides between overlapping 2p orbitals to show the pi
bonding (these two lines represent only one bond). I will draw p orbitals as straight lines, on both sides of
an atom, because the students are right; it is easier to visualize the three dimensional shapes this way (the
third drawing below). Of course, you should draw 3D structures the way your instructor wants them
drawn.
I explicitly include two dots for the pi electrons, because I want you to think of those electrons the
way you think of lone pair electrons (remember pushing curved arrows to move electrons in the acid/base
reactions?). Much of the chemistry of pi bond compounds (alkenes, alkynes and aromatics) begins with
these pi electrons. Most of our arrow pushing mechanisms, for these classes of compounds, will begin
with a curved arrow moving from the pi electrons, just as we begin much of the chemistry of heteroatoms
(nitrogen, oxygen and halogens) with an arrow moving from their lone pair electrons.
Alternative ways of drawing 3D structures that are simpler than the above drawing at showing the 3D details.
H2
H C C H H C C H
3D ethyne drawn with p orbitals as lobes (p orbitals with phase

shown in the left structure and without phase in the right structure.
p orbital lobe
is in back of
p orbital lobes the paper.
are in the plane
of the paper. H C C H
p orbital lobe
is in front of
the paper.
3D ethyne drawn with p orbitals as lines and pi electrons explicitly drawn in, in a manner similar
to showing lone pair electrons. In this book I will usually draw pi bonds this way in 3D structures.
We will practice drawing many 3D structures to train our minds to imagine in three dimensions
and to help us understand a topic under discussion, such as parallel p orbitals in resonance, or
understanding a mechanism we are learning for the first time. However, even our simplified 3D
structures are too complicated for drawing structures in typical discussions of organic molecules. Most of
the time our organic structures will be condensed to very simple representations that are quick to draw
and easy to see at a glance. Sometimes we will include letters to symbolically represent the atoms and
sometimes we will merely have lines on the page, almost to the point where the structures become a
foreign language writing system. Some additional ways of drawing ethyne are shown below. Each
subsequent representation puts a greater burden on you to interpret its meaning. Your advantage is that
every non-hydrogen atom you view (carbon, nitrogen, oxygen and halogens) has to be one of the three
shapes we are developing in this topic, so your choices are pretty limited (sp, sp2 or sp3).
Each line represents a bond. While the three simple lines of the triple bond appear equivalent,
H C C H we know that the first bond formed is a sigma bond of overlapping sp hybrid orbitals. The
second and third bonds are overlapping 2p orbitals, above and below and in front and in back.
Since the C-H bonds are single bonds, we know that they are sigma bonds too, using hybrid
orbitals. This is how you will determine the hybridization of any atom in a structure. Knowing
how many pi bonds are present will tell you how many 2p orbitals are being used in those pi bonds.
The remaining s and 2p orbitals must be mixed together in hybrid orbitals (in this example, only
an s and a 2p remain to form two sp hybrid orbitals).
HCCH The connections of the atoms are implied by the linear way the formula is drawn. You have to
fill in the details about the number of bonds and where they are from your understanding of each
atom's bonding patterns. A C-H bond can only be a single bond so there must be three bonds
between the carbon atoms to total carbon's normal number of four bonds. This means, of course,
that the second and third bonds are pi bonds, using 2p orbitals, leaving an s and p orbitals to mix,
forming two sp hybrid orbitals.
A bond line formula only shows lines connecting the carbon atoms and leaves off the hydrogen
atoms. Every end of a line is a carbon (two in this drawing) and every bend in a line is a carbon
(none in this drawing). You have to figure out how many hydrogen atoms are present by
substracting the number of lines shown (bonds to non-hydrogen atoms) from four, the total number
of bonds of a neutral carbon (4 - 3 = 1H in this drawing). The shape of the carbon atoms must be
linear, because we know the hybridization is sp.
C2H2 This is the ultimate in condensing a structure. Merely writing the atoms that are present and how
many of them there are provides no details about the connectivity of the atoms. It only works for
extremely simple molecules that have only one way that they can be drawn. Ethyne is an example
of such molecule. Other formulas may have several, hundreds, thousands, millions, or more ways
for drawing structures. Formulas written in this manner are usually not very helpful.
carbon atom shape = linear
hybridization = sp All of the details in this group
go together. If you have any
bond angles about sp carbon = 180o one of them, you should be able
number of sigma bonds = 2 to fill in the remaining details.
Molecular Orbitals of Ethyne
We made two very simple molecular orbitals using hydrogen atoms (σ and σ*) and p orbitals (π
and π*) above. The process works pretty much the same when we are making bonds using carbon and
hydrogen atoms (…and nitrogen, oxygen and halogen atoms)? Let’s quickly develop the molecular
orbitals for ethyne. First we need to form the sigma and sigma-star MOs between the two carbon atoms
using their sp hybrid orbitals (σcc and σ*cc). The vertical scale represents relative potential energy among
the various orbitals. Lower is more stable.
sigma-star
antibond,
has a node
higher, σCC∗ = spa - spb = antibonding MO C C

less stable
spa spb
potential C
energy C
lower,
more stable
σCC = spa + spb = bonding MO C C
(2) - (0) = 1 bond sigma

bond order = 2 bond
Next we need to form sigma and sigma-star MOs between each carbon atom and a hydrogen atom
using each carbon atom’s other sp hybrid orbital and a hydrogen atom’s 1s atomic orbital (σCH and σ*CH).
We’ll just show one MO diagram and you can imagine doing it twice.
sigma-star
Two C-H sigma/sigma-star MOs form. This scheme
antibond,
shows one of them. The other would look just like it. has a node
higher, σCΗ∗ = sp - 1s = antibonding MO C H

less stable
sp
potential C H
energy
1s
lower,
more stable
σCΗ = sp + 1s = bonding MO C H
(2) - (0) = 1 bond sigma

bond order = 2 bond
Finally we need to form two pi and pi-star MOs between the carbon atoms using carbon 2p
orbitals (πCC and π*CC). We’ll just show one MO diagram and you can imagine doing it a second time.
This is going to look almost exactly like our example of a pi bond presented earlier.
node
πCC∗ = 2p - 2p = antibonding MO C pi-star

C
antibond
higher, 2p 2p
less stable
potential
energy C C
lower,
more stable
pi bond
πCC = 2p + 2p = bonding MO C C
(2) - (0) = 1 bond

bond order = 2
If we put all of the molecular orbitals of ethyne together, in a single energy diagram, it would look
as follows. The pi MOs determine the highest occupied and lowest unoccupied molecular orbitals
(HOMO and LUMO). The 2p orbital overlap is the least bonding and the least antibonding. The HOMO
electrons are the easiest place to donate electrons from (least tightly held) and the LUMO orbital is the
best place to accept electrons, if accepted into the molecular orbitals (lowest potential energy empty
orbital = most stable of the empty orbitals). The pi molecular orbitals determine much of the chemistry of
alkynes.
MO diagram one σ∗CC antibonding MOs

for ethyne
two σ∗CH antibonding MOs
higher,
less stable Best place to
LUMOs two πCC∗ antibonding MOs
donate electrons to.
potential energy of orbitals
energy on isolated atoms
lower, Best place to take

more stable HOMOs two πCC bonding MOs electrons from.
two σCH bonding MOs

bond order (6) - (0)
between the = = 3 bonds
2
carbon atoms
one σCC bonding MOs
This represents 1/3 of the bonding pictures you need to understand. I hope it wasn’t too painful.
We need to extend this approach two more times for sp2 and sp3 hybridized atoms.
2. sp2 hybridization
Our second hybridization example mixes the 2s orbital with two 2p atomic orbitals, creating three
2
new sp hybrid orbitals. One 2p orbital remains unchanged, and it will help form a pi bond. The relative
energy scheme showing electron promotion and orbital mixing is almost the identical to the sp hybrid
example above. The major difference is the mixing of a second 2p orbital, which alters our hybrid creations
from linear to planar. As above, promoting a 2s electron allows for four bonds to form and allows the
carbon atom to acquire the neon Noble gas configuration. As mentioned in the example of sp hybridization,
electrons in sp2 orbitals are held more tightly than electrons in 2p orbitals, but less tightly than electrons in
2s orbitals. Among atoms of the same type, an atom’s relative electronegativity is dependent on the amount
of 2s character [2s (100% s) > sp (50% s) > sp2 (33% s) > sp3 (25% s) > p (0% s)].
mix (2s and two 2p's),

promote a 2s three ways to create
2p's electron to a 2p's three sp2 hybrid orbitals 2p
2p orbital
sp2 sp2 sp2
2s 2s
sp2 arrangement for a carbon
isolated carbon atom
(not typicalin our world) atom bonded to other atoms,
one p orbital remains to become
part of a pi bond
higher,
less stable
cost = promotion energy ≈ 100 kcal/mole

potential
Overall, this would gain = electron/electron repulsion in s ortibal is removed ≈ 20-40 kcal/mole
energy gain = two additional bonds are possible ≈ 150-200 kcal/mole
be a favorable trade.
gain = more directional orbitals form, that have better overlap of electron
lower, density between the bonding atoms, thus forming stronger bonds
more stable
Creating the sp2 hybrid orbitals
Because two 2p orbitals lie in a plane, the three sp2 hybrid creations will also lie in a plane. The picture
below shows one possible example of orbital mixing. Two additional combinations are necessary (not
shown). Dividing a plane (same as a circle = 360o) into three equal divisions forms 120o bond angles
between the orbitals, where the sigma bonds will be. This allows the electrons in the sigma bonds to be as
far apart in space as possible and minimizes the electron/electron repulsion. The descriptive term for this
shape is trigonal planar. The hybrid orbitals will form sigma bonds and the p orbital will usually form a pi
bond.
mathematically,
mix three ways
2s sp2a
2px and 2py one example of
mixing 2s+2p+2p The "mixing" process symbolized
Similar phase mixes here is repeated two additional ways,
constructively in the creating three sp2 hybrid orbitals.
right front quadrant
sp2b
120o
All three sp2 hybrid orbitals lie
in a plane and divide a circle into
sp2c 120o
three equal pie wedges of 120o.
The descriptive term for the shape
is trigonal planar.
sp2a 120o
top-down
view
120o
C 120o This picture shows the sp2 hybrid orbitals without their small backside
lobes and no p orbital is shown. These hybrid orbitals will form sigma bonds.
120o
The complete picture of an sp2 hybridized carbon atom
An isolated sp2 hybridized carbon atom for viewing.

A bonded carbon atom would need orbital overlap These represent sp2a hybrid orbitals. The
for each orbital present, sp2a, sp2b, sp2c and 2pz. small, opposite phase lobe on the backside
has been left off to simplify the picture.
sp2c 2pz
sp2a
side-on C
view
sp2b There remains one 2p orbital
perpendicular to the three sp2
hybrid orbitals. The 2p orbital
extends along the entire axis with
opposite phase in each lobe.
There are more convenient alternative methods of drawing a three dimensional sp2 carbon atom,
using simple lines, dashed lines and wedged lines. The first drawing below shows the lobes of the 2p
orbital with its relative phases. The second drawing shows the lobes, but not the phases. The third
drawing uses only simple lines instead of lobes for the p orbitals. It is quicker to draw, obscures less
background, yet still shows the directionality of the 2p orbitals, which is an important feature of
resonance.
C C C
sp2 hybridized carbon atom sp2 hybridized carbon atom sp2 hybridized carbon atom
We will use this approach.
Two sp2 carbon atoms bonded in a molecule of ethene (…its common name is ethylene)
As in our sp example, the simplest possible way to place our sp2 carbon atom into a neutral
molecule is to bring another sp2 carbon atom up to overlap with two of its atomic orbitals: a sigma bond
using an sp2 hybrid orbital, along the bonding axis of the atoms and a pi bond, using the 2p orbital. The
pi bond lies above and below the carbon-carbon sigma bond, in the plane of the paper, the way we have
drawn it. Four additional sigma bonds can form around the outside of the two carbons using the
remaining sp2 hybrid orbitals. The easiest bonding arrangement is to bond four hydrogen atoms, using
their 1s atomic orbitals. As with ethyne, this way of drawing a three dimensional structure is too
cumbersome for routine use.
H H
C C
H H
We will draw our 3D structures using more simplified representations. Each sp2 carbon atom has
trigonal planar geometry, with 120o bond angles. Our 3D representations include simple lines to indicate
bonds in the plane of the page, wedges to indicate bonds extending in front of the page and dashed lines
to indicate bonds extending behind the page. Possible 3D drawings are shown below.
H H H H H H
C C C C C C
H H H H H H
2p orbitals drawn as 2p orbital drawn as lobes, 2p orbitals drawn as lines,

lobes, with phase indicated without phase indicated no phase indicated. This
will be our method of
drawing 3D structures
carbon atom shape = trigonal planar

hybridization = sp2 All of the details in this group
As with ethyne, some additional ways of drawing ethene are shown below. Each subsequent
representation puts a greater burden on you to interpret its meaning. Your advantage is that every non-
hydrogen atom you view (carbon, nitrogen, oxygen and halogens) has to be one of the three shapes we are
developing in this topic, so your choices are pretty limited (sp, sp2 or sp3).
H H Each line represents a bond. While the two simple lines of the double
H H
bond appear equivalent, we know that the first bond formed is a sigma
C C ...or... C C
bond of overlapping sp2 hybrid orbitals. This means, of course, that
H H
H H the second bond is a pi bond, using a 2p orbital, leaving an s and two 2p
orbitals to mix, forming three sp2 hybrid orbitals.
The connections of the atoms are implied by the linear way the formula is drawn. You have to
H2CCH2 fill in the details about the number of bonds and where they are from your understanding of each
or atom's bonding patterns. A CH2 forms two single bonds, so there must be two bonds between
CH2CH2 the carbon atoms for carbon's normal number of four bonds. The second bond has overlapping 2p
orbitals, above and below the bonding axis and means the carbon must be sp2 hybridized.
(none in this drawing). You have to figure out how many hydrogens are present by substracting
the number of lines shown (bonds to non-hydrogen atoms) from four (the total number of bonds
of a neutral carbon (4 - 2 = 2H in this drawing).
This is the ultimate in condensing a structure. Merely writing the atoms that are present and how
C2H4 many of them there are provides no details about the connectivity of the atoms. It only works for
extremely simple molecules that have only one way that they can be drawn. Ethene is an example
of such molecule.
We won’t build all of the molecular orbitals for ethene from scratch since the process is essentially
the same as that used for ethyne. However, we will provide a complete molecular orbital energy diagram,
showing all of the sigma and sigma-star MOs and the pi and pi-star MOs. There are now five sigma
bonds (four C-H and one C-C) and one pi bond (C=C). As is usually the case when a pi bond is present,
the pi / pi-star orbitals form the important HOMO / LUMO molecular orbitals. The 2p orbital overlap is
the least bonding (HOMO) and the least antibonding (LUMO). The HOMO electrons are the easiest
place to donate electrons from (it holds the highest potential energy electron pair = most reactive of the
full orbitals), and the LUMO orbital is the best place to accept electrons into ( it is the lowest potential
energy empty orbital = least unstable of the empty orbitals). Most of the chemistry of alkenes uses these
orbitals.
MO diagram one σ∗CC antibonding MO

for ethene
four σ∗CH antibonding MOs
higher,
less stable LUMOs one πCC∗ antibonding MO Best place to
donate electrons to.

Best place to take

lower, HOMOs one πCC bonding MO electrons from.
more stable
four σCH bonding MOs

between the = = 2 bonds
2
carbon atoms
one σCC bonding MO
This completes the second of our three bonding pictures you need to understand. We need to
extend this approach one more time with sp3 hybridized atoms.
3. sp3 hybridization
Our final example of hybridization mixes the 2s orbital with all three 2p atomic orbitals, creating
four new, equivalent sp3 hybrid orbitals. The three 2p orbitals fill all three dimensions and the four sp3
hybrid orbitals created from them also fill all three dimensions. There are no π bonds, since no 2p
orbitals remain to make them. All of the bonds are sigma bonds, because all of the bonding orbitals are
hybrid orbitals. Your intuition about the bond angles probably fails you in this example (it fails me), so
we’ll just accept that the bond angle between sp3 orbitals is approximately 109o (…and if you are really
good at trigonometry, you can figure the exact bond angle out for yourself). We won’t worry about the
exact bond angle (109o 28’ = 109.5o) since there is a considerable amount of variation about the 109o
value in different molecules. The atomic shape of sp3 carbon atoms is described as tetrahedral, but not
because of the shape about the carbon atom, as was the case in our previous two examples. The
descriptive term for the shape of an sp3 atom is based on a geometric figure drawn by connecting the ends
of the sigma bonds. A four sided figure of equilateral triangles is generated, called a tetrahedron. The
energy scheme below is a hypothetical process to get sp3 hybridized carbon from atomic carbon.
As mentioned in the examples of sp and sp2 hybridization, electrons in sp3 orbitals are held more
tightly than electrons in 2p orbitals, but less tightly than electrons in 2s orbitals. Among atoms of the
same type, an atom’s relative electronegativity is dependent on the amount of s character [2s (100% s) >
sp (50% s) > sp2 (33% s) > sp3 (25% s) > 2p (0% s)]. The relative electronegativity of hybridized carbon
increases with increasing percent 2s contribution: sp > sp2 > sp3.
mix (2s and three 2p's),

promote a 2s four ways to create
2p's electron to a 2p's four sp3 hybrid orbitals
2p orbital
sp3 sp3 sp3 sp3
2s 2s
sp3 arrangement for carbon
isolated carbon atom
(not typicalin our world) atom bonded to other atoms,
no 2p orbitals remain so no
higher, pi bonds can form
less stable
potential cost = promotion energy ≈ 100 kcal/mole

energy Overall, this would gain = electron/electron repulsion in s ortibal is removed ≈ 20-40 kcal/mole
be a favorable trade. gain = two additional bonds are possible ≈ 150-200 kcal/mole
gain = more directional orbitals form, that have better overlap of electron
lower, density between the bonding atoms, thus forming stronger bonds
more stable
Creating the sp3 hybrid orbitals
One example of a picture of orbital mixing is provided. Three additional combinations are used to
create the other three sp3 hybrid orbitals, but it is more difficult to show this with our simplistic
representations than it was for sp hybridization. The bottom line is that four atomic orbitals are mixed
four ways to generate four equivalent sp3 hybrid orbitals. An example of all four sp3 orbitals is shown
using our simple 3D conventions: a simple line indicates a bond in the plane of the page, a wedged line
indicates a bond extending in front of the page and a dashed line indicates a bond behind the page. A
tetrahedral figure is also drawn to show where the descriptive geometric term comes from.
mathematically,
mix four ways
y
2s 2px , 2py , 2pz One example is shown of

x sp2a
mixing 2s+2p+2p+2p to
form an sp3 hybrid orbital. The "mixing" process symbolized
here is repeated three additional ways,
Similar phases interact constructively creating four sp3 hybrid orbitals.
in the front, right, upper octant where
the large lobe will be located.
C
C C
=
sp3 orbitals minus A tetrahedron has four equivalent triangular sides.

the small backside sp3 orbitals drawn using
The atoms at the ends of the bonds with carbon
lobes our 3D conventions define the vertices of the tetrahedron. The carbon
is sitting in the middle of the tetrahedron.
One sp3 carbon atom bonded in methane and two sp3 carbon atoms bonded in ethane
In both of our previous examples, we needed two carbons in order to form a pi bond, using the
unhybridized 2p orbitals. Hydrogen atoms don’t have available p orbitals in the n = 1 shell and cannot
form pi bonds. Since sp3 carbon atoms only make single bonds, this is our first example of hybridization
where we can surround a carbon atom with only hydrogen atoms (four of them).. This forms a molecule
of methane, CH4, one of the simplest organic molecules we will encounter. Notice there is only one type
of bond now (σCH) and the HCH bond angles about the central carbon atom are 109o (plus a little bit that
we ignore). This angle allows the electrons in the sigma bonds to be as far apart in space as possible,
minimizing the electron/electron repulsion. The atomic shape is designated as tetrahedral. Since sp3
atoms fill all three dimensions, there is no choice but to use our 3D drawing conventions (simple lines,
dashed lines and wedged lines).
H
H carbon atom shape = tetrahedral
hybridization = sp3 All of the details in this group
H C go together. If you have any
H number of pi bonds = 0
If we remove one of the hydrogen atoms of methane and replace it with the simplest possible
carbon atom, CH3, we would form molecular ethane. Ethane has two sp3 carbons connected by a single,
sigma bond. The six hydrogen atoms in ethane occupy all three dimensions. The single bond between
the two carbons allows rotation to occur and the three hydrogen atoms on one carbon atom can rotate past
the three hydrogen atoms on the other carbon, like the spokes on a wheel. If you have models, why not
build ethane and rotate the C-H bonds about the carbon-carbon axis to see how they move? The different
shapes have slightly different potential energies, and this will be important to us in a later topic
(conformational analysis).
H H
H H H
C C C-C single
H bond rotation C C
H H H
H
H H
A single bond allows rotation to
occur about the carbon-carbon
bond, which alters the shape and carbon atom shape = tetrahedral
the energy of the molecule. hybridization = sp3 All of the details in this group
As with ethyne and ethene, there are some additional ways of drawing ethane. Some of these are
shown below. Each subsequent representation puts a greater burden on you to interpret its meaning.
Your advantage is that every non-hydrogen atom you view (carbon, nitrogen, oxygen and halogens) has
to be one of the three shapes we are developing in this topic, so your choices are pretty limited (sp, sp2 or
sp3).
H H
Each line represents a bond. Since there are only single bonds, we know that they must be
H C C H sigma bonds. There cannot be any pi bonds becasue there are no second or third bonds
between the same two atoms. The 2s and all three 2p orbitals must all be mixed, meaning
H H that the hybridization has to be sp3 and all of the terms that go along with sp3 hybridization.
The connections of the atoms are implied by the linear way the formula is drawn. You have to fill
H3CCH3 in the details about the number of bonds and where they are located from your understanding of each
or atom's bonding patterns. A CH3 has three single bonds between carbon and hydrogen, so there can
CH3CH3 only be one additional bond between the carbon atoms to total carbon's normal number of four bonds.
This means, of course, that there is no pi bond, using a 2p orbital, leaving the 2s and all three 2p orbitals
to mix, forming four sp3 hybrid orbitals.
(none in this drawing). You have to figure out how many hydrogens are present by substracting
the number of lines shown (bonds to non-hydrogen atoms) from four (the total number of bonds
of a neutral carbon (4 - 1 = 3H on each carbon atom in this drawing).
This is the ultimate in condensing a structure. Merely writing the atoms that are present and how
C2H6 many of them there are provides no details about the connectivity of the atoms. A structure can be
generated only for extremely simple molecules that have only one way that they can be drawn.
Ethane is an example of such molecule.
As with ethene, we won’t build all of the molecular orbitals for ethane from scratch, but we will
provide a qualitative molecular orbital energy diagram, showing all of the sigma and sigma-star MOs.
There are no pi and pi-star MOs in ethane. There are now seven sigma bonds (six C-H and one C-C) and
zero pi bonds. The important HOMO / LUMO orbitals have to be sigma and sigma-star MOs in this
example (our designation of relative sigma energies is arbitrary). Because there are no pi / pi-star HOMO
/ LUMO molecular orbitals, ethane is much less reactive than ethyne and ethene.
one σ∗CC antibonding MO

MO diagram
for ethane
LUMO
six σ∗CH antibonding MOs
higher,
less stable

lower, HOMO
more stable
six σCH bonding MOs

between the = 2
= 1 bond one σCC bonding MO
carbon atoms
This represents the last of our bonding pictures that you need to understand. Almost every
example of hybridization used in this book, whether carbon, nitrogen, oxygen or the halogens will use one
of these three shapes. I hope you can see how important this is to your organic career (…and your
biochemistry career).
Summary – Key features to determine hybridization of atoms in organic chemistry.
Use multiple bonds to determine the hybridization state of an atom. A second bond between two
atoms is always made up of 2p orbitals, as part of a π bond, which leaves 2s+2p+2p to hybridize as sp2. If
a third bond is present between the same two atoms, or if a second pi bond is present with a second atom,
it also is made up of 2p orbitals, which leaves 2s+2p to hybridize as sp. If there are only single bonds,
then all four atomic orbitals (2s+2p+2p+2p = sp3) must be mixed together. Essentially, the hybridization
state is determined by subtracting any p orbitals of pi bonds from the three 2p orbitals available for
hybridization. Whatever is left over is mixed with the 2s to form hybrid orbitals. If you know the
hybridization, then you know the bond angles, the shape and how many sigma and pi bonds are present.
What you need now is lots of practice.
There are no second or third bonds between the same 2s 2p 2p 2p

two atoms so no 2p orbitals are used to make any pi bonds.
C C The hybridization must be sp3 (2s + 2p + 2p + 2p = sp3) No pi bonds so all atomic orbitals
3
and all four atomic orbitals are mixed to form four sp are used in hybridization = sp3
hybrid orbitals.
There is a second bond between the two carbon atoms.

This must be a pi bond and uses 2p orbitals. The 2s 2p 2p 2p
C C hybridization must be sp2 (2s + 2p + 2p = sp2) and three
atomic orbitals are mixed to form three sp2 hybrid One pi bond, so only the 2s and two of
orbitals the 2p's are used in hybridization = sp2
There is a second and a third bond between the same two

atoms. There must be two pi bonds using two 2p orbitals. 2s 2p 2p 2p
The hybridization must be sp (2s + 2p = sp) and two atomic
C C orbitals are mixed to form two sp hybrid orbitals. Two pi bonds, so only the 2s and one of
the 2p's are used in hybridization = sp
There is a second bond with the atom on the left and again
with the atom on the right. There must be two pi bonds using 2s 2p 2p 2p
two 2p orbitals. The hybridization must be sp (2s + 2p = sp) and
C C C two atomic orbitals are mixed to form two sp hybrid orbitals. Two pi bonds on center carbon, so
The hybridization of the end carbons, is sp2 (see the second only the 2s and one of the 2p's are
example above). The planar shapes of the atoms of the two used in hybridization = sp
sp2, see above o
end carbons are twisted 90 relative to one another because
the 2p orbitals on the middle carbon making the pi bonds with
them are angled at 90o relative to one another.
We will be viewing and drawing many complicated structures in this book, as we work on
problems and try to understand organic chemistry. To simplify this process, we will often use bond-line
formulas. We have mentioned bond-line formulas, very briefly above, but now we will examine how they
work using all of the features just discussed. The first structure drawn below shows all of the carbon
atoms and hydrogen atoms. The second structure is a 2D Lewis structure. It takes some time to include
such detail. Bond-line formulas allow us to more quickly draw such a structure without all of those
atoms. The down side is that your organic knowledge has to be more sophisticated to interpret what they
mean. Recall that every end of a line and every bend in a line is a carbon atom. We will also use the
convention that a large “dot” in the structure is a carbon atom (see the structure below). Since hydrogen
atoms are deliberately left out, for drawing convenience, you must determine the number of hydrogen
atoms present in bond-line formulas by subtracting the number of bonds shown from four, the usual
number of bonds on a neutral carbon atom.
Number of hydrogen atoms on a carbon = (4) – (number of bonds shown)

(you don’t see these)
See if your interpretation of the bond-line structure is the same as the more detailed structures
provided. As an experiment, time yourself drawing this structure all three different ways, then multiply
the difference in time by the number of structures you will draw during your organic career. I’m sure
you’ll agree that it’s worth the effort to understand bond-line formulas.
H
13
H3C
H H
14 11 H C H
12 13
H3C C CH2
12
H C C C H
CH 10 14 11
H2 H H HH 10 C H
H H
2 C 4 C 6 C 8 1 2
1 C 3 C 5 C 7 C H C C C C C C C C C
H2 H 3 4 5 6 8
C CH2 7 9
H 9 H H H H
Two structures showing all of the atoms. It's a lot of work to draw structures this way.
13
14 12
11
10
3 5
2 4 6 8
7
1
9
Same molecule using a bond-line structure showing only non-hydrogen bonds. A carbon atom is
implied at every bend and every end of a line and every dot. This one is a lot easier and faster to draw.
number of
Carbon # hybridization bond angles shape hydrogen atoms
1 sp 180o linear 1
2 sp 180o linear 0
3 sp3 109o tetrahedral 2
5 sp2 120o trigonal planar 1
8 sp 180o linear 0
Problem 12 - What is the hybridization of all carbon atoms in the structure below? What are the bond
angles, shapes, number of sigma bonds, number of pi bonds and number's of attached hydrogen atoms?
Bond line formulas are shorthand, symbolic representations of organic structures. Each bend represents a
carbon, each end of a line represents a carbon and each dot represents a carbon. All carbon/carbon bonds
are shown. The number of hydrogen atoms on a carbon is determined by the difference between four and
the number of bonds shown.
atom hybridization angles # H's shape

1
2
3
7
3 4
4 2 5
8
5
1 6
6
11
13 15 7
9 12 14 8
10 9
16
10
17
11
12
13
14
15
16
17
Other Atoms in Organic Chemistry – nitrogen, oxygen and halogens
Here is a perfect example of why you want to learn the logic and patterns of organic chemistry,
and not use brute force memorization as a strategy. We still have a number of other elements to cover.
How do these other atoms fit into the hybridization models developed above for carbon? Except for
hydrogen, which only has 1s electrons and no hybrid orbitals, all of the other atoms are similar to carbon.
There are a few minor differences mentioned earlier in this book. Nitrogen adds another proton for a Zeff
of +5 and has five valence electrons. Oxygen also adds another proton for a Zeff of +6 and has six valence
electrons (sulfur behaves similarly). Fluorine adds yet another proton for a Zeff of +7 and has seven
valence electrons (Cl, Br, I are similar).
Fully bonded neutral atoms of carbon, nitrogen, oxygen and fluorine all have an octet of valence
electrons. However, this is accomplished in different arrangements of bonds and lone pairs of electrons
(nonbonded electron pairs). Carbon makes four bonds and has zero lone pairs, nitrogen makes three
bonds and has one lone pair, oxygen makes two bonds and has two lone pairs and fluorine makes one
bond and has three lone pairs. The increase in Zeff through this series makes each subsequent atom hold
on more tightly to its valence electrons (higher electronegativity, F > O > N > C).
A lone pair of electrons can often be considered just like a sigma bond in determining the
geometry about an atom. As such, it would occupy a hybrid orbital. However, when a lone pair is next to
a 2p orbital, either as part of a pi bond or an empty 2p orbital, the lone pair orbital changes its shape to
that of a 2p orbital in order to spread out electron density and stabilize the structure by minimizing
electron/electron repulsion and lowering its potential energy. As near as I can tell, this is one of the more
difficult ideas to learn for beginning organic students.
In this book, resonance is a concept used to show how electron delocalization can occur.
Resonance occurs in multiple parallel 2p orbitals, and it requires you to see and draw in two and three
dimensions, so that you can recognize when parallel 2p orbitals are present. Parallel 2p orbitals allow
delocalization of electron density through those parallel 2p orbitals. You also need to recognize formal
charge (discussed below), and to use the concept of electronegativity to help evaluate the relative
contributions of the various resonance structures. It is important that you are able to work with pi bonds
and resonance structures, because they explain so much that happens in organic chemistry and
biochemistry.
Even with all of these differences, nearly every single atomic shape that we study, will be one of
the three hybridization states developed above for carbon. The following table shows almost every
possibility of neutral atoms that you will see in organic chemistry. We will quickly add formal charge to
our repertoire and find that all of the cation and anion possibilities also use one of our three different
hybridizations. This is almost too good to be true – but it is!
Valence Possibilities for Neutral Atoms
Atom sp3 sp2 sp sp # bonds # lone pairs Zeff ∆χ
carbon C C C C 4 0 +4 2.5
too
nitrogen N N N many 3 1 +5 3.0
bonds
too
oxygen O O many 2 2 +6 3.5
bonds
too
fluorine F many 1 3 +7 4.0
bonds
H too
hydrogen many 1 0 +1 2.2
(1s orbital)
bonds
Problem 13 - What types of orbitals do the lone pair electrons occupy in each example above, according
to our hybridization model? Hint: What is the hybridization of the atom? It has to use the same kind of
hybrid orbital to hold the lone pair electrons…unless it is part of a resonant system.
Problem 14 – Can a nitrogen atom bond in the second sp pattern above for carbon (four bonds)? Can an
oxygen atom bond in the first sp pattern above for carbon (three bonds)? How about the second sp
pattern of carbon (four bonds)? Can a fluorine atom bond in the sp2 pattern for carbon (two bonds)? Are
any of these reasonable possibilities? Have you ever seen a structure with four bonds to a nitrogen atom
or three bonds to an oxygen atom or two bonds to a fluorine atom? Would there be any necessary
changes for the atoms in such arrangements? We’ll discuss the answers to these questions soon.
Our bond-line structures are changed, just a bit, when heteroatoms are present. A heteroatom is an
atom different than carbon or hydrogen (for us heteroatoms will be nitrogen, oxygen, sulfur and the
halogens). All heteroatoms are explicitly drawn in, as well as any hydrogen atoms attached to the
heteroatoms.
Problem 15 - What is the hybridization of all nonhydrogen atoms in the structures below? What are the
bond angles, shapes, number of sigma bonds, number of pi bonds and number of hydrogens not shown?
How many lone pairs are on each atom and in what kind of orbital are they located? As with carbon, use
the number of pi bonds to determine how many 2p orbitals are not mixed in the hybrid orbitals. Mix the
remaining orbitals to determine the hybridization, which then answers the remaining questions.
a.
18
17
16
14
O O 15
13 H 19
4 5 N 22 23
7 O
3 6 F
21
8
2 N 10 9 NH2
1 20
N 11
12 24 OH
25
hybridization of
atom hybridization angles # H's shape # lone pairs lone pair orbital
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
b.
18
O
21
22 20
F 19 H
13 5
4 N 16
11 O 17
10 3
9
8 6 N 2
7 1 14 N
OH 15
12
hybridization of
atom hybridization angles # H's shape # lone pairs lone pair orbital
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Formal Charge
Formal charge calculations help us track valence electron credit in chemical structures. This
system of rules allows us to calculate if an atom in a molecule, ion or free radical has a normal, an excess
or a deficient allotment of electron density. Calculations can be applied to resonance structures, showing
how charge is spread out over the structure, which in turn, can provide clues about how stable a substance
might be or how it might react in a chemical reaction. Formal charge calculations can also be applied to
reactants and products in chemical reactions, providing insight into how those reactions proceed, by
showing where new bonds have formed and where old bonds have broken.
Formal charge calculations assume that any valence electrons in bonds are shared evenly between
the bonded atoms, even if it’s an oxygen atom bonded to a hydrogen atom or a carbon atom. This means
if there is a single bond, each atom gets credit for one of the electrons, if there is a double bond each atom
gets credit for two of the electrons, and if there is a triple bond each atom gets credit for three of the
electrons. Formal charge calculations also assume that atoms having lone pair of electrons gets full credit
for those electrons.
An atom’s total share of valence electrons (bonded and lone pairs) is compared with the opposing
positive charge from the Zeffective of that atom. The formal charge on an atom is assigned by using the
following equation.
protons in the nucleus

Formal electrons in
balancing an atom's 1 electrons in
Charge = lone pairs
normal contribution to 2 covalent bonds
the valence electrons
This number never changes for Total valence electrons - This number varies
an atom and represents positive depending on the bonding arrangement. It is
charge, Zeff. negative because electrons are negative.
The first term in the equation is a positive number and represents Zeffective, the portion of the
positive charge in the nucleus that balances an atom’s usual number of valence electrons. Zeff is always
the same for a particular type of atom and is equal to an atom’s group number in the periodic table (B =
3A, C = 4A, N = 5A, O = 6A and F = 7A). The second term credits all of an atom’s lone pair electrons to
its formal charge calculation. The third term assumes that electrons in bonds are shared evenly between
atoms, as stated above, and multiples the total number of bonded electrons by ½. The second and third
terms are negative because they indicate the number of valence electrons credited to an atom. If an
atom’s Zeff is balanced equally by an atom’s share of valence electrons, there is zero formal charge. If an
atom has more electron credit than Zeff, it will have an extra negative formal charge for each extra
electron. If an atom has less electron credit than its Zeff, it will have a positive formal charge for each
deficient electron. The equation is easier to use and remember, if you understand the logic contained
within it.
Concise Rules of Formal Charge
1. When an atom’s total valence electron credit exactly matches its Zeff, there is no formal charge.
2. Each deficiency of electron credit from an atom’s normal number of valence electrons
produces an additional positive charge.
3. If the formal charge calculation shows excess electron credit over an atom’s normal number of
valence electrons, a negative formal charge is added for each extra electron.
4. The total charge on a molecule, ion or free radical is the sum of all of the formal charges on the
individual atoms.
Rules of Formal Charge, with examples
1. When an atom’s total valence electron credit exactly matches its Zeff, (“unshielded protons in the
nucleus”) there is no formal charge. The normal number of valence electrons can also be determined
from the group number of the column in the periodic table.
2. Each deficiency of electron credit from an atom’s normal number of valence electrons produces an
additional positive charge (cationic).
This can happen in many different ways. Some of those ways are shown in several examples
below, though other ways are possible (e.g. there are no one electron transfers shown). Chemical
reactions can occur in a single step or in multiple steps. Most of the individual steps, even in multi-
step reactions, involve a transfer of two electrons from an electron pair donor to a target atom
(electron pair acceptor) that subsequently gives up two electrons to another atom, which then takes
those electrons away. Typically, there are at least three atoms involved in this process. Each
participant has a special name. The electron pair donor is a Lewis base, but in organic chemistry it
also goes by the term “nucleophile”. The electron pair acceptor is a Lewis acid, and it also goes by
the term“ electrophile”. Finally, the atom or group that takes away the electrons is called a leaving
group. You will see these terms countless times in your organic chemistry and biochemistry careers,
so learn them well.
Lewis base = nucleophile = electron pair donor
Lewis acid = electrophile = electron pair acceptor
leaving group = takes away excess electron density from an electrophile
Usually, bond formation (electron pair donation) and bond breakage (electron pair removal), step
1 and step 2 of the first reaction below, occur approximately simultaneously, but sometimes the steps
are sequential. When step 1 and step 2 are sequential either bond formation can occur first or bond
breakage can occur first. When bond formation occurs first, an atom’s valency must increase by two
electrons. This is impossible for carbon, because that would violate the octet rule (but is possible at
atoms that can expand their valency). We will never see reactions like this at carbon. However, there
are reactions at carbon where bond breakage occurs first. We will study reactions where the first
broken bond is a sigma bond and reactions where the first broken bond is pi a bond.
Generic Examples of Organic Reaction Steps
Four very general, and common, views of reaction steps in organic chemistry are shown below.
Notice how formal charge changes as the reactions proceed in the generic examples below. Creation
of positive charge indicates a loss of electron credit (e.g. 0 Æ +1), or becoming less negative (e.g.
–1 Æ 0), through loss of a lone pair or sigma electrons or pi electrons. Creation of negative charge
(e.g. 0 Æ -1), or becoming less positive (e.g. +1 Æ 0) indicates a gain of electron credit. Gained
electrons can show up as an additional lone pair of electrons or a gained sigma or pi bond at a
particular atom. Pay special attention to how curved arrows are used to show electron movement in
the reactions that follow. In the general examples 1-3 that follow, Y is often some form of carbon in
organic chemistry, but there are plenty other atoms that can react in this manner. In example 4,
carbon atoms are explicitly drawn and Y can be a variety of possibilities, including carbon.
In the reactions below, full headed, curved arrows indicate two electron movement in the reactants
that shows how the products will form. The straight arrows in these examples are pointing to a related
part of a structure that is being discussed in the narrative below the arrow.
Example 1 - Steps 1 and 2 are approximately simultaneous.
1 2
X
Y Z X Y Z
"X" donates The target atom,"Y", accepts and
electrons and The new sigma bond The lone pair of
gives up electrons by breaking a between X and Y came
makes a new sigma bond, allowing Y and "Z" to electrons on the
bond with "Y". from the nucleophilic leaving group, Z,
separate. "Y" is an electrophilic lone pair of electrons of X.
We call X a atom. "Z" takes electrons away came from the
nucleophile. and is called a leaving group. This former sigma bond
is usually necessary to maintain a between Y and Z.
Noble gas configuration at "Y".
Example 2 - Steps 1 and 2 are approximately simultaneous.
1
2
X
Y Z X Y Z
"X" donates "Y" accepts and gives up electrons

The lone pair of electrons on
electrons and by breaking a pi bond. Y and Z to The new sigma bond Z came from the pi bond
makes a new remain attached through the sigma between X and Y came between Y and Z. The sigma
bond with "Y". bond. "Y is an electrophilic atom. from the nucleophilic bond remains so there isn't a
We call X a "Z" takes electrons away, but since lone pair of electrons leaving group.
nucleophile. it does not actually separate from Y, of X.
is not called a leaving group.
Removal of the pi electrons is
necessary to maintain a Noble gas
configuration at "Y".
Example 3 - Steps 1 and 2 are sequential. Such reactions at carbon require bond breaking before
bond making (a sigma bond breaks in this example).
a. step 1 1
Y Z Y Z
δ+ δ-
"Y"gives up electrons by breaking a polar
sigma bond, allowing Y and "Z" to separate. Y has become electron The lone pair of electrons
deficient and highly on Z came from the former
"Z" takes electrons away because it is the reactive, as it needs a sigma bond between Y and Z.
more electronegative atom. "Z" is a leaving lone pair of electrons. Usually, Z must be pretty
group, but there is no nucleophile or electrophile Y is an electrophile, and stable as an anion or neutral
yet. Y+ will become an electrophile after Z when Y is a carbon atom it molecule, for this to happen.
is also called a carbocation. Z is called a leaving group.
leaves and will trap a nucleophile, X:, in a
subsequent step.
b. step 2
2
X Y X Y
"X" donates two electrons and makes a The new sigma bond between X and Y came from
new bond with "Y", completing its octet. the lone pair of electrons of X. In a common variation
X is a nucleophile. The electrophile, Y, of this step, the donated electrons can come from a pi
does not have a leaving group because bond, similar to the next example. There may be an
Z already left in the previous step. additional step, not shown here, to disipate the positive
charge on X.
Example 4 - Steps 1 and 2 are sequential. Carbon-carbon pi bonds often react in this manner
(alkenes, alkynes and aromatic compounds). From the point of view of Y-Z this reaction is not much
different than example 1. However, from the point of view the electron pair donor (the pi bond), it is
quite different. The donated electrons in this example are shared between two atoms, while in
example 1, the lone pair electrons belonged to a single atom, X:. In this example one of the carbon
atoms will lose its shared pi electrons. This feature is more similar to the first step of example 3,
where sigma electrons are lost by atom Y. Those electrons will have to be added back in a subsequent
step of electron donation. In this example “R” represents any general organic possibility.
a. 1
R R 2
R R
Ca Cb Y Z Ca Cb Y
Z
R R
R R
A CC pi bond donates The target atom,"Y", accepts
electrons, which breaks electrons from the pi bond and The new sigma bond The lone pair of
the pi bond. The pi gives up electrons by breaking between Cb and Y came electrons on Z came
electrons make a new a sigma bond between Y and Z, from the pi electrons of from the former sigma
bond with "Y". The allowing Y and "Z" to separate. the C=C pi bond. Ca is bond between Y and Z.
CC pi bond is a Y is an electrophilic atom. "Z" left electron deficient and
nucleophile. takes electrons away and is a needs a pair of electrons.
leaving group. Removal of the
sigma electrons is necessary to
maintain a Noble gas configuration
at "Y".
b.
R R
R R
Ca Cb Y
Z R Ca Cb Y
R R 3
Z R
"Z" donates electrons to "Ca, making a new sigma bond. "Ca"is The new sigma bond between Ca and Z
a carbocation and is an electrophile. There is no leaving group came from the lone pair of electrons of Z.
because Ca has an incomplete octet. By reacting with Z, Ca regains
its octet of electrons. Nucleophilic Z is used here for convenience.
Another electron pair donor could have supplied the necessary electrons
to complete the valency of Ca. X: was used in the other examples 1-3.
Specific Examples of Organic Reaction Steps
The examples below are more specific to organic chemistry and biochemistry. One purpose of
showing these reactions here is to feature an important aspect of formal charge. A second purpose is
to get you thinking that many organic reactions have common themes in their reaction paths. Your
organic quest is to discover these common themes and learn them.
Example 1 - An atom (oxygen, below) shares one of its lone pairs with another atom (a proton is a
common target). You will see this happen many times in acid/base reactions. X takes two electrons
away, because it is usually pretty stable on its own as a leaving group.
1 2
3 4
R O H
H X R O
X
H H
alcohol,
Lewis base, Lewis acid, protonated alcohol, leaving group
nucleophile electrophile conjugate acid conjugate base of HX,
1. A neutral alcohol molecule, ROH, reacts as a Lewis base and a nucleophile by donating an
electron pair (this is a more "organic chemistry" way to think about the reaction) "R" indicates
a generic carbon group.
2. H-X reacts as a Lewis acid and an electrophile by accepting an electron pair (the organic way
of thinking).
3. The oxygen atom used one lone pair to form a new bond with a proton, so those electrons are
now shared in a covalent sigma bond. Oxygen's electron credit went down by one electron.
The positive charge shows that this oxygen is electron deficient (0 Æ +1).
4. Atom X, the leaving group, gained one lone pair (0 Æ -1). These electrons were formerly
shared in a covalent sigma bond. X’s electron credit went up by one electron. The negative
charge shows that X is now electron rich. Usually X is pretty stable on its own, as an anion or
as a neutral molecule, if “H-X” had a positive charge (e.g. H3O+).
Example 2 - Similar to a, except the oxygen atom is sp2 hybridized in a carbonyl group (C=O).
2
R 1 3
R H 4
C O
H X C O X
R
R
carbonyl group, Lewis acid, protonated conjugate
Lewis base, electrophile carbonyl group base of HX
nucleophile
1. A neutral oxygen atom from a carbonyl group (C=O) reacts as a Lewis base and a nucleophile
by donating a lone pair (organic focuses on electron pairs). X must remove two electrons to
maintain hydrogen’s Noble gas configuration.
2. H-X reacts as a Lewis acid and electrophile by accepting an electron pair.
3. The oxygen atom used one lone pair to form a new bond with a proton, so those electrons are
now shared in a covalent bond. Oxygen's electron credit went down by one electron. The
positive charge shows that this oxygen is electron deficient.
4. Atom X, the leaving group, gained one lone pair. These electrons were formerly shared in a
covalent sigma bond. X’s electron credit went up by one electron. The negative charge shows
that X is now electron rich.
Example 3 - The protonated carbonyl group (C=O+-H) from example 2 has a useful resonance
structure that shows why the carbon atom carries a significant portion of the positive charge. This
makes the electrophilic carbon a good target for attack by a nucleophilic lone pair of electrons (from
the alcohol oxygen atom, here), just as hydrogen was attacked in the previous two examples. The
bond broken in this reaction is the carbon-oxygen pi bond. The carbon and oxygen atoms do not
separate because the sigma bond remains to hold them together. The sequence of events, however, is
the similar to the previous two examples: 1. electron pair donation to a target atom to make a bond, 2.
electrons are lost by the target atom and 3. an atom takes an electron pair away when the former bond
is broken. Notice how the reactant alcohol oxygen atom has acquired a positive formal charge in the
product. The protonated alcohol is now ready to undergo the same sort of reaction as H-X of example
1. (Lewis base attacks the proton and makes a sigma bond with the proton as the alcohol oxygen atom
leaves with a pair of electrons.)
R H
C O
R
resonance
1 R H R R H
R O 3
C O
O C O
H R 2
H R
alcohol, protonated addition product of alcohol and
Lewis base carbonyl group, protonated carbonyl group
nucleophile Lewis acid,
electrophile
1. A neutral alcohol (ROH) oxygen atom reacts as a Lewis base and nucleophile by donating a
lone pair of electrons (partially negative) to the partially positive carbon atom.
2. The carbon of the protonated carbonyl group reacts as a Lewis acid and electrophile by
accepting an electron pair at carbon, forcing the pi electrons to the partially positive oxygen
atom, which becomes neutral. This allows the carbon atom to maintain its Noble gas
configuration and allows oxygen to regain its full credit of electron density. There is no
leaving group in this step, only leaving electrons.
3. The alcohol oxygen atom that donated its lone pair formed a new bond with the carbon atom,
so those electrons are now shared in a covalent bond. That oxygen atom's electron credit goes
down by one electron. The positive charge shows that this oxygen has become electron
deficient (0 Æ +1). The carbonyl oxygen atom gained an extra electron pair, so its electron
credit went up by one and its positive charge went down by one to neutral (+1 Æ 0). Notice
how the positive charge shifted from the carbonyl group to the alcohol oxygen atom.
Example 4 – The carbon of a neutral carbonyl group (C=O) can also be attacked by a lone pair of
electrons, if the electron pair donor is strong enough. The carbanion shown here is one of the
strongest electron pair donors known. We will study many examples of this type of reaction. Notice
the similar sequence of events: 1. electron pair donation to a target atom to make a bond, 2. electrons
are lost by the target atom and 3. an atom takes an electron pair away when the former bond is broken
(a pi bond, here).
R
C O
R
resonance
3
H
1 R
H R
H C
C O
H C C O
H R 2
H R
carbanion, carbonyl group,
Lewis base, addition product of
Lewis acid, carbanion and carbonyl group
nucleophile electrophile
1. The carbanion reacts as a Lewis base and a nucleophile by donating an electron pair to the
partially positive carbon atom of the carbonyl group (C=O).
2. The carbon of the carbonyl group reacts as a Lewis acid and electrophile by accepting an
electron pair, forcing the pi electrons to the oxygen atom, which becomes negatively charged
and maintains a Noble gas configuration at carbon. Moving the minus charge from carbon to
oxygen is, generally, a good thing. There is no leaving group in this reaction, only leaving
electrons.
3. A new sigma bond is formed between the carbanion carbon atom and the carbonyl carbon
atom. The carbanion carbon's electron credit goes down by one electron, becoming neutral
instead of negatively charged (-1 Æ 0) and oxygen’s electron credit goes up by one, becoming
negatively charged (0 Æ -1).
Example 5 - Carbon-carbon pi bonds occur in alkenes, alkynes and aromatic compounds. It is useful
to think of pi electrons as Lewis bases and nucleophiles. They are closely analogous to lone pairs of
electrons, that we explicitly draw. If you recall, I did ask you to explicitly draw them in our 3D
structures of pi bonds. If you reexamine example 1 above, you can see how similar these two
examples are.
R 1 R 2 3
R R 4
C C
H X C C H X
R R
R R
C=C pi bond of an alkene, Lewis acid, conjugate
alkyne or aromatic functional protonated pi bond
electrophile forms carbocation base of HX
group, Lewis base, nucleophile
1. A neutral pi bond reacts as a Lewis base and nucleophile by donating an electron pair from its
pi bond. There is some similarity to example 1. However, only one of the carbon atoms of the
pi bond keeps the electrons. The other carbon atom loses those electrons, and becomes an
electrophilic carbocation. This part is different from example 1.
2. HX is a Lewis acid and electrophile, and reacts by accepting an electron pair.
3. One carbon atom used the pi electrons to form a new sigma bond with a hydrogen atom, so
these electrons are retained and now shared in a covalent sigma bond with that hydrogen atom.
This carbon atom's electron credit stays the same and it is still neutral (0 Æ 0). The other
carbon atom's electron credit goes down by one electron, since it lost its electron when the pi
bond reacted (0 Æ +1). The positive charge shows that this carbon atom is electron deficient.
A carbon atom like this is called a carbocation and is a strong Lewis acid and electrophile.
4. Atom X gained one lone pair; electrons which were shared in a covalent bond. Its electron
credit went up by one electron (0 Æ -1). The negative charge shows that X is now electron
rich. In many organic reactions of this type, X will turn around and donate its nucleophilic
electrons to the electrophilic carbocation, in a subsequent step.
Example 6 - An atom (carbon, below) loses two shared electrons from a covalent sigma bond that is
broken. This reaction does not follow the patterns presented above where two electrons are donated
and two electrons are lost simultaneously (two arrows in a single equation). In this example there is
subsequent step that brings in two electrons to replace the electrons that were lost from carbon.
Step 1 1 2
R R 3
R C Br R C
Br
R
R
bromide
bromoalkane carbocation leaving group
Step 2
4 R
R
R C O R R C O R
R H R H
carbocation, alcohol, protonated ether
Lewis acid, Lewis base,
electrophile nucleophile
1. In step 1, the C-Br sigma bond is broken, with the more electronegative bromine atom taking
both electrons with it. Bromine is the leaving group. This leaves a very electropositive carbon
atom with only three sigma bonds and positive formal charge.
2. Carbon's electron credit went down by one when the sigma bond was broken and bromine took
away both of the shared electrons (0 Æ +1). The positive charge shows that this carbon is
electron poor and needs two electrons to complete its octet. A carbon like this is called a
carbocation. Carbocations are strong Lewis acids and electrophiles. Two electrons will be
added back to the carbon in a subsequent step (step 2). Later, we will discover that these
electrons are added back in, in one of three possible ways.
3. The bromine atom gained an additional lone pair from the electrons that were shared in the
carbon-bromine sigma bond. Bromine's electron credit went up by one electron (0 Æ -1). It is
more electron rich as bromide.
4. In step 2 the electrophilic carbon lacking an octet is an obvious target for donation of a
nucleophilic pair of electrons from the oxygen atom of the alcohol. The alcohol is a Lewis
base and nucleophile. The positive charge moves from electropositive carbon to
electronegative oxygen. At first this does not look like a good trade off, but the positively
charged oxygen atom has a full octet, while the positively charged carbon had only six valence
electrons. The full octet trumps the relative electronegativity differences. Also, if you count
all of the sigma bonds in the reactants (five) you will see that an additional bond is created in
this reaction step, as there are six sigma bonds in the products. It’s always better to have more
bonds. The product of step 2 looks ready to donate a proton (it’s a strong acid), similar to
examples 1,2 and 5 above (…and it does).
Take another look at the example reactions above and contemplate what the curved arrows and
formal charge are showing you. You might even consider placing those examples in front of you as
you eat your morning breakfast and “meditating” on them. As you study the reactions in this book,
you will see these ideas again and again and again…
This has been a long detour from formal charge rule 2 to rule 3, but a lot of important material was
previewed. You are not expected to understand the details of the above reactions – yet (…except
formal charge). All of these reactions, and more, will be studied in detail later in this book. Do try to
see the similar features in each of these reactions. Seeing the similar themes is the secret to making
sense of organic chemistry and biochemistry…and will make your life so much more enjoyable.
3. If the formal charge calculation shows excess electron credit over an atom’s normal number of
valence electrons, a negative formal charge is added for each extra electron (anionic). There are a
number of ways that this can occur. Several of them are shown in the examples above. Electrons can
be retained by an atom from a broken sigma bond or a broken pi bond, giving an atom excess electron
density and negative charge if it was neutral to begin with (0 Æ -1). If the atom that retains the
electrons had a positive charge as a reactant, it would become neutral in the product structure (+1 Æ
0). In either case, formal charge will show that the atom gained electron density (neutral Æ negative
or positive Æ neutral).
4. The total charge on a molecule, ion or free radical is the sum of all of the formal charges on the
individual atoms. The overall charge on a molecule can be neutral, even though formal charge is
present on specific atoms in its structure, if the charges cancel one another. Examples demonstrating
this aspect in organic chemistry are shown below.
H H O
H
C N N H C N
H C N N N O O O
H H O
H
The overall formal charge The overall formal charge The overall formal charge The overall formal
on diazomethane is 0. on nitromethane is 0. on azidomethane is 0. charge on ozone is 0.
Amino acids typically have formal charge present. Three examples are provided showing multiple
charges totaling zero, negative one and positive one.
H
H
N C
O O
N H
C C
H H O H H C
H
H C O
H N C C
H CH2 O
H N C C
H H O
H N C C
H H O
H H O
glycine aspartic acid histidine
overall charge = 0 overall charge = -1 overall charge = +1
Most of us like well-defined, unambiguous methods for solving problems, and the formal charge
equation above will do this for you in this. However, the formal charge calculation is tedious to do over
and over for every atom in a structure. As you use this equation, your intuition will grow. You will begin
to recognize that when an atom gains an electron pair from what was a bond (sigma or pi), it becomes
more negative by one, and when an atom shares an electron pair by making a bond (sigma or pi), it
becomes more positive by one. If a sigma bond breaks and an atom keeps the electrons, it becomes more
negative by one, while the atom that lost the electrons becomes more positive by one.
Knowing what an atom’s normal bonding pattern is makes it easier to recognize when it’s not
normal and what the difference is (e.g. H3O+ has fewer lone pairs than water and HO- has more lone pairs
than water). As a quick reminder of neutral atom bonding patterns, hydrogen atoms always form one
bond, carbon atoms form four bonds, nitrogen atoms form three bonds and have one lone pair or
electrons, oxygen atoms form two bonds and have two lone pairs of electrons (sulfur often bonds
similarly) and fluorine atoms form one bond and have three lone pairs of electrons (the other halogens
bond similarly).
In the following formal charge problems you will find many structures similar to those you will
see on your journey through organic chemistry. You may instantly recognize the formal charge in some
of these, or you may be flummoxed by the formal charge on an atom. When you don’t know what the
formal charge is, use the above equation to calculate it. However, first try to use your intuition to
speculate upon an atom’s formal charge. When you find that you are consistently correct on your guesses
at formal charge, it is probably safe to begin using your intuition to estimate formal charge. This will
happen naturally from your experience of working many problems. The formal charge equation is always
there, whenever you feel puzzled about an atom’s formal charge.
As you work through the problems, you will see that some of the structures have been grouped
together and have identical skeletal arrangements and overall formal charge. The only difference between
the grouped structures is where the formal charge is placed and where the pi bonds are drawn. These are
resonance structures, which are necessary variations to show how charge is distributed in a given
structure. In many organic structures, a single 2D or 3D representation cannot show the actual charge
distribution. Resonance structures are used to collectively reveal where charges (or partial charges) are
located. A double headed arrow is placed between all resonance structures to indicate what they are. We
will discuss this topic more in the next section and it will be used often throughout this book. This is just
a little up-front notice about one your most important concepts.
Before we actually calculate a formal charge, I need to make a disclaimer. When we write a
positive charge on oxygen in H3O+, it seems that oxygen is carrying the entire load of the positive charge.
What it really means is that the oxygen atom is electron deficient relative to a normal oxygen having two
bonds and two lone pairs of electrons. When we write a negative charge on hydroxide, HO-, we really
mean that the hydroxide oxygen atom is carrying a larger amount of electron density than a “neutral”
oxygen atom. Computational calculations can estimate the amount of positive and negative charges
present on each atom in a molecule or ion. If we perform such calculations on hydroxide, water and
hydronium ion (thanks Herb), we find that in all of them the oxygen atom carries a partial negative charge
that is balanced by the positive charge of the hydrogen atoms (H3O+ and H2O) or hydrogen atom (HO-).
Even in H3O+, there is no positive charge on the oxygen atom. What we can see is that the oxygen atom
is less negative in the hydronium ion than water and less negative in water than in hydroxide.
Formal charge is useful to us, if we just remember that it indicates an electron deficiency or an
excess of electron density on an atom compared with its neutral bonded state. An electron poor oxygen in
H3O+ induces a base to attack a proton, which then releases the electrons in the O-H sigma bond to the
oxygen atom, so that it has the usual amount of electron density it needs. Electron deficient atoms will
tend to attract negative charge towards them and electron rich atoms will tend to push their electron
density towards positive sites. It is somewhat paradoxical that in all of the structures that we study,
hydrogen atoms will always have one bond and zero formal charge, even as they carry the partial positive
charge, when bonded to electronegative atoms like nitrogen, oxygen or the halogens.
δ-
δ+ δ+
H O H O H H O H H O H
H H
δ+
formal charge = -1 formal charge = 0 formal charge = +1
Calculated Perhaps a more accurate

Calculated Calculated
partial charges partial charges partial charges way to represent H3O+,
but not as practical for
oxygen = -1.214 oxygen = -0.664 oxygen = -0.291 drawing structures.
hydrogen = +0.214 hydrogen = +0.332 hydrogen = +0.430
Problem 16 – Write in the formal charge wherever present in the atoms below. Resonance structures are
shown within parentheses and have double headed arrows between them. All of the resonance structures
must be considered together to evaluate the true nature of a particular structure.
Row 1 methyl methyl methyl methyl methyl

methane free radical carbocation carbanion singlet carbene doublet carbene
H H H H
H H
H C H H C H C
H C H C H C
H H
H H
Row 2 H
H N H H N H H N H N N H N H
H H H H
Row 3
H O H H O H H O O H O
Row 4 H H
H F H H F F F C F C F
H H
H H H H
Row 5
C C C C C C H
H C C H H C C
H H H H H
Row 6
H C N C N H2C C N H 2C C N
Row 7
H C N H H C N H H C O H C O
H H H H H
Row 8
O N C N C N C N
H H H H H H
Row 9 H H H
H
C O C O C O
H B H B H H N B H
50% 40% 10%
H H H H theoretical calculation of relative contributions.
Row 10
O O O O O O
O S O S O S O S
S S
O O O O Cl Cl Cl Cl
The first two structures violate the octet rule, but are often rationalized based on sulfur's 3d orbitals to accept additional
electron density. The first structure of the second group also violates the octet rule. Not all chemists agree on this point.
Row 11 O O O O
H3C S O H H 3C S O H3C S O H 3C S O H3C S
O O O O
Row 12
F F O O
F B F B H 2C N H 2C N
F F O O
Row 13 O O
O O
H 3C N H3C N
O O O O
O O
Row 14 H H H H
O O
H C O H H C O H C O H
C C
H H H H H H
H
Row 15 O O O
H H
O O C H C H C H
H N H N H N
C C
H H H H H H H
Row 16 H H H
O O O O O
C C C H C H C H
H N H N H N H N H N
H H H H H
H O O
Row 17 H H
O O
O
C C
C CH3 H C H C
C CH3 C CH3
H O H H
H O H O
H H
Row 18 H H H H
H C O H C O H C O H C O
C C C C C C C C
C N C N C N C N
H C H H C H H C H H C H
H H H H
Row 19 O H O H O H
C C C C C C
H C CH2 H C CH2 H C CH2
H H H
Which atoms from row 19 would you suspect are most likely to donate electrons in a chemical reaction?
Problem 17 - Which connection of atoms appears to be more reasonable in each pair below? Why?
Assume that all nonhydrogen atoms have full octets. That means you have to add in lots of lone pairs of
electrons. Some of these structures have different connections of the atoms (they are isomeric) and some
have the same connections of the atoms, but have different electron distributions (they are resonance
structures). Can you tell the difference?
a. b.
H C N C N H H Cl O Cl O H
c. O O d. H O O
N O N O C O C O
H H H H H
e. H O O f. H O O H
N O N O C N C N
O O H H H H H
h. H O H O
g. H O H O H
C N C N
C C C C H
H H H H
H H H H
Problem 18 – Add in any necessary formal charge to atoms in the equations below and then add in curved
arrows to show electron movement in bond formation and bond breakage (review problem 10 on page 21
and the examples starting on page 52). Two arrows are required on the left side of each equation. Which
atom donates electrons in each of the following chemical equations and what atom accepts those
electrons? What is the polarity of each atom in the bond forming reaction? Do the products support your
answers? Classify the reactants as Lewis acids and bases, and as electrophiles and nucleophiles.
a.
H O H Cl H O H Cl
b.
H H H H
H N + H C Br H N C H + Br
H H H H
c.
H
H H H
H N C O H N C O
H H
H H
Problem 19 – Even relatively simple formulas require clues about the connectivity of the atoms. These
clues can come from the way a structure is drawn or from a chemical name. Using a very simple formula,
CH3NO2 , some possible sigma skeletons have been generated. How many total valence electrons are
there for bonding and lone pairs? (1xC, 1xN, 2xO, 3xH = ? electrons) Is there any formal charge? In
some examples below, it depends how you add in the electrons. One way generates structures without
formal charge and another generates structures with formal charge. These are called resonance structures,
(developed in the next topic) Are there pi bonds, rings or lone pairs? Count the number of sigma bonds
in the bottom row and compare it to the number of sigma bonds in the top row. In which row do we find
resonance structures? What type of orbitals are necessary for resonance structures? (Hint: They are
found in pi bonds.) There should be the same total number of bonds and lone pairs in every structure.
This row has potential resonance structures.

a b c d e
H O H O H
O O H H O O
O H
C N C N H C N H C O N N C
H H H H O H H O H
This row does not have potential resonance structures.

g H
f h i H j
H O H
O H N O
O H N H O
C H C N
N C O C O C N H
H O H H O
H H H O

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Chapter 1 Benzene Blues 27

The Hybridization Model of Atoms in Molecules

Carbon as our first example of hybridization

1. sp hybridization – carbon and other atoms of organic chemistry

mix (2s and 2p), two

Creating the hybrid orbitals

The Complete Picture of an sp Hybridized Carbon Atom

Carbon has one electron

Ethyne has five total bonds: three

These terms all go together. For neutral sp carbon,

3D ethyne drawn with p orbitals as lobes (p orbitals with phase

Molecular Orbitals of Ethyne

higher, σCC∗ = spa - spb = antibonding MO C C

(2) - (0) = 1 bond sigma

higher, σCΗ∗ = sp - 1s = antibonding MO C H

(2) - (0) = 1 bond sigma

πCC∗ = 2p - 2p = antibonding MO C pi-star

(2) - (0) = 1 bond

MO diagram one σ∗CC antibonding MOs

lower, Best place to take

two σCH bonding MOs

mix (2s and two 2p's),

cost = promotion energy ≈ 100 kcal/mole

Creating the sp2 hybrid orbitals

The complete picture of an sp2 hybridized carbon atom

An isolated sp2 hybridized carbon atom for viewing.

2p orbitals drawn as 2p orbital drawn as lobes, 2p orbitals drawn as lines,

carbon atom shape = trigonal planar

MO diagram one σ∗CC antibonding MO

potential energy of orbitals

Best place to take

four σCH bonding MOs

mix (2s and three 2p's),

potential cost = promotion energy ≈ 100 kcal/mole

Creating the sp3 hybrid orbitals

2s 2px , 2py , 2pz One example is shown of

sp3 orbitals minus A tetrahedron has four equivalent triangular sides.

one σ∗CC antibonding MO

potential energy of orbitals

bond order (2) - (0)

Summary – Key features to determine hybridization of atoms in organic chemistry.

There are no second or third bonds between the same 2s 2p 2p 2p

There is a second bond between the two carbon atoms.

There is a second and a third bond between the same two

Number of hydrogen atoms on a carbon = (4) – (number of bonds shown)

atom hybridization angles # H's shape

Valence Possibilities for Neutral Atoms

Atom sp3 sp2 sp sp # bonds # lone pairs Zeff ∆χ

protons in the nucleus

Concise Rules of Formal Charge

Rules of Formal Charge, with examples

Lewis base = nucleophile = electron pair donor

Lewis acid = electrophile = electron pair acceptor

leaving group = takes away excess electron density from an electrophile

Generic Examples of Organic Reaction Steps

Example 1 - Steps 1 and 2 are approximately simultaneous.

Example 2 - Steps 1 and 2 are approximately simultaneous.

"X" donates "Y" accepts and gives up electrons

Specific Examples of Organic Reaction Steps