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ORGANIC CHEMISTRY 307

Fall 2017
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 i-
clicker, the online instructional support (OWL, eBook) and Chem Draw.
These documents may be found in the Miscellaneous folder in Resources.

How to Succeed in Organic Chemistry

Much of the emphasis in General Chemistry is on numerical problem
solving. To a large extent your results in that course were determined by
your problem solving skills.
The emphasis in Organic Chemistry is on different active skills. Because the
exams are not multiple choice to any significant extent, you will need to be
able to do things to succeed.

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 won’t always parallel your textbooks. Read them before
you read the textbooks. Do not read the book until after you have read the
relevant lecture notes. Then read the assignments in the textbooks before the
lectures, focusing on the things that are emphasized in the lecture notes.
Come to lectures, then reread the textbooks and the notes, do the homework,

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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. Remember, it’s not enough
to understand the answer. You must also master the skills that lead to the
answer. Looking at a structure and “understanding” it, is not the same thing
as being able to draw the structure.

4. In addition to the assigned homework, you will find some explanations
and a large number of additional problems (some with solutions, all with
answers) in a folder called “How to Solve” in the Resources section of the
Sakai site. This material covers primarily the early part of the course and is
from a manuscript for a possible book called “How to Solve Organic
Chemistry Problems.” There are likely still some errors in this material. If
you find one, please bring it to my attention. Your help will be appreciated
and noted.

5. 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 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. The Sakai site has the exams from
the six previous years posted. You will notice that the exams are similar
from year to year. They are an extremely valuable study tool. You can use
them most effectively by taking an exam under testing conditions (90
minutes in a quiet room) and then using the key to grade your paper.
6. Use recitations, review sessions, office hours, email, Facebook, etc. to
get help and answers to your questions. We are committed to providing you
as much help as possible.
7. 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. Look around.

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(50 years ago there were fewer than 1 million) In addition there are over 66 million genetic sequences known. as far as Wohler (who did the experiment) could tell. The first in a series of key experiments that led to its abandonment was the preparation of urea from apparent inorganic sources. each one is a different organic compound. almost magical ingredient called Vital Force. was abandoned in the 19th century. most of them organic. B. 3. except for a very few that have only a C-C bond or a C-X bond(X conventionally means halogen). 1. We shall briefly look at some organometallic compound because of their importance in the synthesis of other organic compounds. but not all compounds that contain carbon are organic. 2. mysterious substance associated with living things. There is. That number is increasing every day. What’s so special about Carbon? Why are there so many compounds of Carbon? Review the material on the Periodic Table. C2O4H2 (1 C-C bond) are. in which the organic compounds also contain at least one metal atom. Technically. This urea was indistinguishable from urea from animals. one reason why Organic Chemistry is required for majors in the life sciences. There are more than 100 million chemical substances known. Most of the organic compounds we will consider in this course consist of only nonmetals. related to “organism” or life. So compounds such as sodium bicarbonate or calcium carbonate are not defined as organic compounds. This connotation is mostly historical and comes from the fact that virtually every chemical of life is organic. a large important branch of organic called organometallic chemistry. Therefore all samples of a given pure organic substance are the same regardless of their origin. Historical: The Vital Force Theory. But compounds such as carbon tetrachloride CCl4 (4 –Cl bonds) or oxalic acid. 4. But the difficulty of proving that something doesn’t exist is the reason that it took many more experiments and many years before everyone was finally convinced that there was no magical. which postulated that any substance from a living thing had a special. We shall use this one: Organic compounds all have at least one C-H bond. A pure synthetic vitamin is the same as a pure natural one. Organic chemistry is often defined as the chemistry of compounds of carbon. Most known chemical compounds are organic. organic chemistry has a different connotation. [oversimplified all organic compounds contain carbon.] To some extent definitions such as these are arbitrary or historical. the electronic 3 . To some laypersons. however.

In the middle of the second row. Position in the Periodic Table. Any energy cost of changes in orbitals is more than offset by the formation of bonds and octet completion. d. which is not very different from the C-C bond energy. which are two or more carbon atoms linked together [One of the first skills you must master is to be able to draw these chains and understand how they are put together. 1. It is an unnecessary and inaccurate complication. The 4 electrons from C plus the 4 electrons from the atoms to which the C bonds result in a noble gas electronic configuration around the C. The valence shell electron configuration of carbon is 2s22p2. Has 4 valence electrons. But the C-O bond energy is 358 kJ/mol. e. so it’s small (can get close to other atoms and form multiple bonds) and in the middle of the EN scale. Most compounds of carbon contain such chains. Thus C is good at forming covalent bonds.] b. 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 that are part of chains. 2. Just remember carbon has 4 valence electrons and therefore forms 4 bonds. That speaks to stability. c. 4 . to complete its octet. Look at bond energies. You may have learned about “promotion” in the past to explain the formation of four bonds by C. The most common reagent on Earth is O2. to explain why so many compounds exist that have these carbon chains. But could C-C bonds form something better by chemical reaction? This is a question about reactivity. So C-C bonds are relatively unreactive under ordinary conditions. so it can form 4 covalent bonds by electron sharing with things that bring a total of 4 electrons.configurations of atoms. 3. We need to consider two issues. The bond is strong because of good orbital overlap. stability and reactivity. Remember bond formation is energetically favorable. But. why are there so many compounds of carbon? a. and covalent bond formation in your Gen Chem book. When an atom in a compound is associated with 8 valence electrons we say that the atom has a completed octet. The C-C (bond energy = 347 kJ/mol) is a strong bond. Carbon atoms can form chains. as we shall see.

relative electronegativities. N. 2. O. Valence Shell Electronic Configurations 1. (Note when we compare energies.) This principle has broad applications in Organic Chemistry. O = 2 (and two lone pairs). or three pairs of electrons we have a covalent bond. The formation of covalent bonds is energetically favorable. Aufbau and electronic configuration b. One very simple explanation is based on electrostatics. N = 3 (and one lone pair). Organic cpds with other nonmetals are rare. So there is a favorable interaction between the electrons of an atom and its nucleus. They are all nonmetals and they are all found in organic compounds. The electron is negative and the nucleus is positive. when they are in their lowest oxidation states P = 3. B. the electron interacts favorably with two nuclei. As you already know.Review (Gen Chem) A. X (halogen). Thus in this course we can focus on just a few nonmetals. the two nuclei can’t be too close to each other or their positive charges will repel each other. know their electronic configurations. and S =2 (like O). however. and (less important P and S). 2. The orbitals in the valence shell of a nonmetal are s orbitals and p orbitals. If the atom now shares one of its electrons with another atom. Valence shell is the key. (like N). lower energy is better. Covalent Bonds 1. When an atom does not form the preferred number of bonds. Review and learn the electronic configurations of these important elements: C. two. some of these nonmetals can form other numbers of bonds in some chemical species. In nonmetals the valence shell is made up of the orbitals with the highest value of n. Atomic Orbitals a. For example. H = 1. X = 1(and 3 lone pairs). When two atoms share one. Also. Shells and Subshells. Electron pair sharing. This advantage of electron sharing has limitations based on distance and electron properties. it will have a 5 . H. There are a number of different ways that we can explain it depending on how we choose to describe bonding. Nonmetals tend to form a preferred number of bonds: C = 4. 2. This very important principle operates under the conditions found on the surface of our planet. and other relevant atomic properties and not have to worry about a large number of other elements.

it is very important for us to have useful and easy ways to describe the chemical bonds in a substance. We draw Lewis structures. If you don’t get very good at drawing Lewis structures very soon. I) in the –1 oxidation state = 2 (formal or ionic charge +1). The Localized Bonding Model is the simplest and most familiar. Being able to draw Lewis structures is a vital skill for Organic Chemistry. We will often be permitted to write simplified Lewis 6 . We will use lines to represent shared pairs and dots if necessary to represent lone pairs. Br. It doesn’t change because we choose a different description. When P and S are in their lowest oxidations states (-3 and -2 respectively) they behave like N and O. or that best explains whatever property is of interest to us. C = 4. which tell us what is attached to what and how. O = 3 (formal or ionic charge +1). you will not succeed in 307. Remember: the structure of a molecule is what it is. 3. respectively.1-1. such as X or O. 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. But the other elements can form more bonds than the preferred number without expanding their octets: N = 4 (formal or ionic charge +1). there are a number of different ways to describe bonds. Note that when X is bonded to O. and which provide an accounting of the valence shell electrons.2. When they do so they are in higher oxidation states and bonded to more electronegative elements. charge. Descriptions of Bonding. the preferred number is also the maximum. and F = 1. Since chemical change is the making and breaking of bonds and since the properties of a substance are closely related to its bonding. We refer to such a charge as a formal charge. As we shall see. We choose the description that is most convenient for us.2A-C) and problems in both books and on Sakai to make sure you master this skill as soon as possible. not only if it is part of an ion. 4. X will be in a higher oxidation state and this rule does not apply. BF 1. Use the available material (CP 1. X (Cl. The focus is on the valence shell electron pairs associated with each atom of the chemical species. but even in a neutral compound. Maximum number of bonds: [very important Second Row Elements do not expand octets under ordinary conditions and never in Chem 307-308] For H = 1.

structures. doesn’t change. these structures are called contributing structures and they are imaginary. When we can draw different reasonable Lewis structures with the same skeleton structure for a given compound. 5.) Two equivalent reasonable structures tend to make major contributions to the actual structure. Resonance (CP 1. not the atoms. BF 1. The most important factor is the number of bonds. but are still perfectly clear. There is a discussion in CP1. a.8). They are simply imaginary drawings we have chosen to use to represent the structure of a real substance. The more bonds the better (subject to the limitations of octet expansion.3. contributing structures do not correspond to anything real. the actual compound (or species) is a blend of all the Lewis structures that can be drawn. in order to draw the different structures. the skeleton structure. 7 . (They are drawn without showing the C-H bonds.) Remember that we move only the π electrons and the lone pairs. the more they contribute to the description of the actual structure. When you can draw more than one Lewis structure with the same skeleton structure (what is attached to what) for a species.)The more reasonable the structures. In other words. Consider the following two structures for the acetate ion.3 of what makes a given structure more or less reasonable. what is attached to what. 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. The real structure of a compound that cannot be described by a single Lewis structure is a blend of the contributing structures. 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. Be sure you understand it. (The idea that the most reasonable structures are those with the minimum possible formal charges is called the Principle of Electroneutrality. Remember.

only lone pairs or electrons in pi bonds can undergo this movement in contributing structures. Being able to use these arrows correctly is another essential skill you must have. We will use these arrows not only to generate contributing structures as shown here. If we wanted to show the movement of a single electron we could use an arrow with a single barb. The tail of the arrow points to an electron pair in a given location in a structure. but especially to explain how reactions take place. The head of the arrow points to its new location. We will use such arrows throughout the year to account for real or imaginary (as in this case) movement of electrons. But using these arrows helps us to write the various important contributing structures of a species. given one of them. Here is another example 8 . As you can see. Here the movement of the electron pairs is imaginary because a contributing structure is imaginary. Note the two curved red arrows in the figure. Practice drawing these arrows to generate additional contributing structures. what are called a reaction mechanisms. Being able to draw and use these arrows for contributing structures and reaction mechanisms is an essential skill. These kinds of arrows are used by organic chemists to do electron bookkeeping. from one that you are given. The double barb of the arrow indicates that we are referring to a pair of electrons.

Element Preferred Max # of Formal Fewer # Formal # of bonds Charge of bonds Charge bonds C 4 4 3 -1 H 1 1 no N* and P* 3 4 +1 2 -1 1 -2 O* and S* 2 3 +1 1 -1 F 1 1 no Cl*. 6. Do not use the complex formula that was used in Gen Chem and is in Section 1. in the context of completed. It’s all electron bookkeeping. which is not difficult once you see the overall logic. Learn and understand this table. 9 . but they are both reasonable. (Later on we will consider species in which an element does not have a completed octet). Br*. Formal charges (which are sometimes also ionic charges) can be determined from the number of bonds. but not expanded octets. The table below shows the relation between number of bonds and formal charge for elements with completed octets and no octet expansion. It will be very useful. unless octets are not complete.2D of BF. Just learn this table. Notice that these two contributing structures are not identical. I* 1 2 +1 no * In their lowest oxidation states.

Often. So. Leave out the dots but leave in most of the dashes. named after a famous 19th century organic chemist. Lewis Structures are based on preferred number of bonds. c. It must be if you need to include dots. Structures without the dots are sometimes called “Kekulé” structures. Note that we 10 . but we need shorthand to keep things manageable. C. (See how many you can draw) b. They tell us what is attached to what and how. They show all the valence shell electrons. we need some information about the compound to draw the Lewis Structure. for example. which tells us that there is an O-H attached a C=O. If you decide to include the dots on a given atom. N = 3. But be careful. and X (halogen) = 1) and have completed octets. a carboxylic acid). (Define). a. (C = 4. These rules tell us what is attached to what in our shorthand structures. you must include all of them (unless instructed otherwise). In this case the information is that it is an acid (actually. composition: C2H4O2 is not a very useful formula in Orgo because of isomerism. bonding pairs as dashes and lone pairs as dots. as here. The shorthand is based on the fact that H always forms just one bond and the other common atoms in neutral organic molecules generally have a fixed number of bonds. Consider acetic acid. We can add to 8. There are at least 10 different structures (without formal charges) that can be drawn with this composition. as we shall see. the structure for water is wrong. O = 2. But drawing a Lewis structure of a compound with many atoms can be tedious. Representations of Compounds and their Structures Very Important What do we want to show? Increasing levels of information about molecular structure.

unless there is no ambiguity. or 1 (You must be able to do this automatically) or accommodate for formal charges. 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 when drawing condensed structures. It could also be CH3CH(CH3)CH3. We can do even more condensing. (or C3H8) or CH3CH2CH2CH3 (but not C4H10. The main (more later) carbon chain is written horizontally with the associated hydrogens generally to the right of each carbon or if the hydrogens are attached to other atoms such as N or O. it will not be so easy for more complex compounds. It is essential that a condensed structure correspond to only one correct molecule and that it can be easily understood. Note: You must practice until you can write and understand these kinds of condensed structures. (just to try to simplify) O C OH H 3C d. f. we can work out the structure. We can add to 4. reflexively and effortlessly. Otherwise we usually include the other kinds of bonds. Note the difference with the formula in Part a. Answer: There are two compounds with this formula. e. We can write CH3CO2H and because we know the preferred number of bonds for the atoms. You must be careful not to leave out so much that there is ambiguity. There are some conventions we tend to follow in drawing these condensed structures. Leave out all the dashes. While we can work out the structure of a simple molecule such as acetic acid from this kind of condensed formula. to the right of them as well. 2. 11 . This approach leaves room for judgment. Other substituents in the middle of the main chain are indicated with vertical lines or parentheses. CH3CH2CH3. So it’s usually okay to include extra information. why?).have also omitted all the bonds to H (C-H and O-H) here. consistent with unambiguity: CH3CH3 (or even C2H6). a condensed representation of .

We will learn other kinds of projections later that work well for specific situations. Below is a projection of ethane. g. ______ This simple line represents ethane. f. So we can go even further when things are unambiguous. So the molecule CH3(CH2)3CH3 can be written as This method of drawing structures is the one we shall use most often (especially on exams) because it is the way our software (Chem Draw) does it. Examples: CH3(CH2)5CH3 or (CH3)4C. 12 . In 2-D we use projection or perspective drawings to give 3-D information. We draw bonds in 3 ways. there is only one C atom at the connection. There is also a document in Sakai Resources called Drawing Structures that you will find very helpful. In a line-angle formula we do not show C and H atoms or even C-H bonds. When two lines meet. h. and in front it is a wedge. The point of the condensed structures is to save space and time. If the bond is in the plane of the paper it is an ordinary line. Geometry and 3-D. A line is a C-C bond with the C at each end assumed to have the correct number of H’s attached. C2H6. Once we are comfortable adding up to 4. in back it is a dashed line. The simplest projection is the dashed (or dotted) line- wedge projection. There are directions on the Sakai course page for downloading this software. we can condense even further. It is an excellent learning tool that can provide you help in a number of areas of the course (and it’s free). We draw the main carbon chain in the plane of the paper. as in propane (C3H8) A zig zag line is a chain of C atoms and the ends are CH3 groups.

More refined and useful descriptions are based on combinations of the atomic orbitals of the valence shell of the atoms. Instead we describe it by designating a region of space around the atom in which there is a high probability of finding the electron. you would not see an orbital. You can think of the electron in a region of space as a standing wave. it is of limited use in helping us understand and predict the properties and chemical behavior of most substances. in place like a guitar string. 1. up and down or side to side. In 3-D use a model. In order to represent conveniently this region of space by a picture. 13 . because of the wave nature of the electron. It can be described by a mathematical function called a wave function. (Learn to use the model kit that came with your textbook. Remember if you could look at an atom or molecule. we can’t pinpoint its exact location. 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 attached to what in molecules. g. Very briefly. like other mathematical functions has a sign (+ or -) that gives us information about relative symmetry. Please review thoroughly and be certain you understand the coverage of orbitals in Gen Chem. The wave function. which is a wave that vibrates. It is just a picture we draw to describe a region of space where an electron may be found. Do not confuse this sign with an electrical or arithmetical sign. but does not propagate like an ocean wave or a light wave. The surface is made big enough so it encloses 90% of the probability of finding the electron. 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).) D.

The opposite signs tell us these portions of the wave have opposite symmetry. 14 . The sign of the wave function is the same everywhere. so we need to focus mainly on the 2s and the 2p orbitals. Hydrogen has only a 1s orbital. 2. and Cl) An s orbital is represented as a sphere. which are given by the l quantum number. S. Most of these are in the second row.sign of the wave function). Of special interest to us are the energies and sizes of orbitals. In order to describe bonding on the basis of combinations of atomic orbitals. Similarly its size increases as n increases. Notice that the wave has crests ( + sign of the wave function) and troughs (. called nodes. as shown by the red color in one lobe and the blue color in the other. Again. which are given mainly by the n quantum number. the shapes of orbitals. We will almost never be concerned with d orbitals (in this course) and rarely with 3s and 3p orbitals (only in P. where the probability is zero. Within the enclosed region of space. There are actually points. Within the enclosed region of space the sign of the wave function may or may not be the same throughout. The wave function has a different sign in each of the two lobes. because we encounter so few elements. whose size increases with an increase in n the principal quantum number. It could also have been a single blue color. A p orbital has two lobes with a nodal plane at the nucleus. as shown by the single red color. we should understand some of the features of orbitals. As we shall see this characteristic of some orbitals can have an important influence on bonding. and the sign of the wave function in different regions of orbitals. the probability of finding the electron is not the same at every point. We need consider only a small number of orbitals in Organic Chemistry. this material was presented in Gen Chem and you should review it.

if two orbitals “combine. Orbitals on different atoms can combine to form molecular orbitals. b. A bond is described by describing the atomic orbital on each atom and how the two combine. These orbitals are called hybrid orbitals. 3. Do not be misled by the word “combine. Each of the three energetically equivalent p orbitals points in a different direction. Notice that unlike spherical s orbitals. For example. Again. a. This rule can be called “conservation of the number of orbitals. An orbital is a picture that we draw to help us represent the structure and properties of a molecule. c.” 15 . remember that if you could look at an atom. 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.” 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. There are certain rules that have to be followed when orbitals are combined. p orbitals are directional.” two new orbitals are formed. which can be the basis for the formation of bonds. Combinations of Atomic Orbitals There are two types of orbital combinations. you would not see any orbitals. The number of orbitals is the same before and after combination.

If two atomic orbitals overlap. each on a different atom. (If it does. One (the good one) is of lower energy than either of the atomic orbitals and therefore the other one must be of higher energy. 4. The decrease in energy is exactly offset by the increase in energy. the result is destabilization). 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. 16 . but the total energy of the orbitals is the same before and after combination. The orbital of higher energy is called the antibonding orbital and does not usually hold even one electron. Thus the total energy of the two orbitals before they combine is equal to the total energy of the two orbitals formed by combination. The two new orbitals will generally not have the same energy as the orbitals that combine. Molecular Orbitals Let’s look first at the formation of molecular orbitals by combination (or overlap) of two atomic orbitals.” iii. a. ii. These relationships are summarized below for the overlap of two 1s orbitals to form H2. 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. two molecular orbitals are formed. This rule can be called “conservation of energy.

which leads to destabilization. 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. An antibonding orbital is a little harder to understand. The pair is most likely to be there because the energy associated with it being in that region of space is low. Remember: Orbitals are just pictures we draw to help us describe electrons in atoms and molecules. It is our picture (not a thing) of another region of space where electrons are allowed to be. But an orbital can only hold two electrons. 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 that’s where the electrons go. such as an antibonding orbital. so an additional electron must be in the high energy antibonding orbital. If you could look at a molecule. Note that combination of two wave functions with the same sign (called constructive interference) produces the bonding orbital and combination of those with opposite signs (called destructive interference) produces the antibonding orbital. 17 . It is our picture of the region of space where the shared pair of electrons is most likely to be. The antibonding orbital (region of space) also comes into play when a molecule absorbs energy. We can understand what a bonding orbital represents. you would not see orbitals.

25) are incorrect. 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. This kind of overlap is the only one possible with an s orbital and can also occur with p orbitals.18. Common sense and experience correctly predict that σ bonds are generally stronger than π bonds because the overlap is better. Find the error. Notice that the figure below from BF (1.11.17. 1.b. which was shown above for H2. So we describe a double bond as one σ bond and one π bond and a triple bond as one σ bond and two π bonds between the two atoms that are bonded.21) and other similar figures in Chapter 1 (1. There can only be one sigma bond between two given atoms. The other is called pi (π) overlap and it can take place between two parallel p orbitals. The bond formed in this way is called a pi bond. The bond formed in this way is called a sigma bond. 1. 18 . One is called sigma (σ) overlap. 1. Two atoms can form one or two pi bonds between them in addition to the sigma bond. The orbitals overlap along the internuclear line. We use two basic pictures to describe how atomic orbitals can combine (or overlap) to form a bond.

but write it as 2sp2. We say there is restricted rotation around multiple bonds (since they consist of at least one π bond). We describe this situation as “free rotation” and it exists for single bonds. We call these two new orbitals 2sp hybrid orbitals. Two or more orbitals on the same atom can be combined to form hybrid orbitals. What is the advantage of hybridization? The hybrid orbital is more directional than either an s orbital (not directional at all. On the other hand. if necessary. Review this Gen Chem material very thoroughly. We use exponents to indicate the composition of the orbital. 5. Hybrid Orbitals. which could be used for a π bond. It will be critical in this course. Suppose we combine a 2s orbital and a 2p orbital that are on the same atom. We form two new orbitals. 19 . Remember the two important rules that apply to combinations of atomic orbitals: conservation of the number of orbitals and conservation of energy. Still remaining on the atom are two unhybridized 2p orbitals. each of which is one part s and one part p. Still remaining is one unhybridized 2p orbital. We call them 2sp2 orbitals. Hybrid orbitals provide a better description of the bonds that the atom forms than a description based just on atomic orbitals. which points equally in two directions. each of which is one part s and two parts p. We can use the remaining unhybridized 2p orbitals to make π bonds if necessary Continuing the same reasoning. These hybrid orbitals are very good for σ bond formation. Since weakening bonds is disadvantageous such rotation generally does not occur near room temperature. which are directional bonds along the internuclear line. There is another consequence of the different geometrical requirements for σ and π overlap. rotation around a π bond does change the nature of the overlap and therefore weakens the bond. it is a sphere) or a p orbital. When two atoms (with their other attached atoms) are connected by a σ bond. Their energy is the average of the energy of the 2s and the 2p that combined to form them. Read it as 2s1p2. rotation around the σ bond does not affect the overlap. we can combine a 2s orbital and two 2p orbitals to make three hybrid orbitals.

If there are two sigma bonds and no lone pairs the atom is sp hybridized. (Remember. In this course we shall opt for consistency and never hybridize terminal atoms. in other words. 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. If the total of sigma bonds and lone pairs is four (2 sigma bonds and 2 lone pairs or 3 sigma bonds and 1 lone pair or 4 sigma bonds). Terminal atoms need not be hybridized. it should be bonded to at least two other atoms. Look at each atom in the molecule. a. when the atom is hybridized. In order for you to call an atom hybridized it should be part of at least two sigma bonds. Thus H and F are never hybridized and the other halogens are never hybridized when bonded to carbon. Using the same notation these four orbitals are 2sp3. other books don’t.) iv. iii. as in a C=O bond or terminal N atoms as in a bond. the lone pairs are in hybrid orbitals. 6. the atom is sp3 hybridized. Either way is an approximation. The situation is more complicated for terminal O atoms. It the total of sigma bonds and lone pairs is three (2 sigma bonds and one lone pair or 3 sigma bonds). Because there is a very close connection between hybridization and bond angles. Properties of Covalent Bonds Let’s look at and apply some of the attributes of covalent bonds presented in Gen Chem that help us describe molecules and understand their behavior. you know what hybrid orbitals it uses to form sigma bonds and to hold its lone pairs. Once you assign a hybridization to an atom. Assign a hybridization by counting the number of sigma bonds and lone pairs. 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. BF does hybridize these atoms. you will be able to predict some of the geometry of a molecule from its hybridization. How do we use hybridization to describe the bonding in a molecule? i. one by one and determine whether or not it is hybridized. ii. the atom is sp2 hybridized. (2s1p3). 20 . those with only one sigma bond.

Use the Electroneutrality principle. chloromethane: CH3Cl. the best structure is the one with the least formal charge. Shorter bonds tend to be better. but that will not always be the case. C-C 347 kJ/mol] but other factors also operate. as we shall see. We describe hybridization and bond angles (and thus molecular geometry) based on an ideal geometry. Indicates how good overlap is. Multiple bonds.What makes a strong bond? Good overlap. why?). Thus smaller atoms tend to form stronger bonds [average bond energies: C-H 413 kJ/mol. 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. c. and linear geometry (bond angles of 180) is the ideal for sp. Let’s apply some of these ideas to an actual molecule. (although double is usually not twice single. i. All the nonmetals except H are more EN than C. Different EN can also be a factor in causing deviations from ideal. Draw the one that looks the best. which have more overlap than single bonds are stronger. Connectivity comes from the preferred number of bonds. 21 . trigonal planar geometry (bond angles of 120) is the ideal for sp2. The ideals are based on the hybridization of an atom.5) is the ideal for sp3. (mostly). which says that absent other information. the more energy it takes to break it and the more energy is released when it forms. There are other factors to be discussed that influence the strength of a bond. but limited by not getting the atoms so close that the nuclei repel each other. Think of bonds as lines connecting the centers of the two atoms attached to each other to understand some other properties. The stronger the bond. Molecules with only strong sigma bonds are generally relatively stable and often relatively unreactive. f. unequal sharing due to EN. Most substances do not have an ideal geometry. which have magnitude and direction. Bond moments. but many are close. d. e. Bond angles VSEPR and hybridization must be consistent. Tetrahedral geometry (bond angles of 109. Review polarity related to chemical behavior from Gen Chem. Also review dipole moments and vector addition of bond moments. There are really no other sensible choices here. Bond length. b.

0 and H-C-H 110. v. Cl is more EN than H. C-H 111 pm. iv Bond Length: C-Cl 178 pm.9. More p character means a smaller bond angle (sp3 is 75% p. 0.86 D compared to C-Cl bond moment. Shown as vectors. bond angle 120). and in the direction of the C. which is 1. but CH3Cl does not because of differences between Cl and H. The electronegative Cl bonds to a hybrid orbital on carbon with more p character.56 D because of the EN difference. because the bonding pair of electrons is not so tightly held by the C. Discuss which orbitals overlap and do not hybridize Cl. The C-H bond moment is small. (1s of H or a 3p of Cl with the 2sp3 orbitals of C) iii Methane has ideal tetrahedral geometry.30 D. When three 22 . Geometry is tetrahedral. Or VSEPR the pair in C-Cl bond is further from the C allowing the other angles to spread. bond angle 109 and sp2 is 67 % p. Where are the electrons? Predict and explain the bond angles: answer: H- C-Cl 108. Hybridization comes from 4 σ bonds around C. Dipole moment is 1. ii. Two rationales.

Geometry is trigonal planar. but in common usage [discuss] ethylene. vi Bond Strength: C-Cl=350 kJ/mol compared to C-F=451 kJ/mol and C-Br=294 kJ/mol.) ii. systematic name ethene. So the result of the three C-H vectors is a vector of magnitude 0. What you would see is a cloud of 4 electrons between the two carbon nuclei. size and EN. It is. by over 50 kJ/mol g. Hybridization comes from 3 σ bonds and no lone pairs around C. The sigma-pi description is not what you would see if you could look at a molecule of ethylene. You would not see two types of electrons. Small size and large EN difference tend to make bonds stronger. 23 . We predict that C-O should be stronger than C-N because of EN. It is. their vector sum is a vector equal in magnitude to one of the three vectors and directed to or from the fourth corner of the tetrahedron. C2H4.vectors of equal magnitude are directed toward or from three corners of a regular tetrahedron. Two factors influence bond strength. Let’s do another. by more than 40 kJ/mol. (Any other option has formal charges. i. We predict that C-H should be stronger than C-C because of size. Connectivity comes from preferred number of bonds.3 pointing toward the Cl. This resultant is then added to the C-Cl vector.

their preparation. Measurements indicate that it is.7 These bond angles can be explained in several ways. v The measured bond angles are indeed not ideal. and bigger. and their properties in general. 7.3 of BF. iv We predict that the geometry is not quite ideal because there are two types of bonds and two types of atoms. 24 . their chemistry. iii We predict the double bond is stronger. The chemical behavior and to some extent the physical behavior of the molecule is determined primarily (but not entirely) by the functional groups. This approach is introduced in Section 1. One of the major challenges of Organic Chemistry is to find a way to organize and systematize an enormous amount of information. which are to a large extent independent of the specific compound. The most common approach to this problem is to classify compounds based on their composition and certain structural features. HCH = 118 and HCC = 121. These parts of the molecule have very little effect on chemical behavior. BF mentions the important ones and you should learn them now. The overall organization of the material in the course will be based primarily on functional groups. Most organic molecules have one or more additional structural features such as multiple bonds or other elements (mostly commonly O or N or X). their interconversions. You should learn the material in these sections now. So we are going to focus on functional groups. It will make things easier for you as we go along. shorter. Any part of the molecule that is something other than a C bonded to other C’s by single bonds and to H’s is called a functional group. 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. Most chemical change takes place at the functional groups. and then to focus on the properties of the structural features. Virtually all organic molecules have carbon-carbon single bonds and carbon-hydrogen bonds.