Organic Chemistry

 Dated mid-1700s; alchemists tried to explain differences between compounds derived from living and
non-living

 Torbern Bergman: expressed the difference between organic and inorganic.

 Organic chemistry: term coined to express the chemistry of compounds from living organisms and
compounds made by humans such as plastics, pharmaceuticals, etc.

Atomic structure

Neutron-help stabilize the nucleus of an atom

Protons-provide the attractive electrostatic central force that binds the atomic electrons

Electrons-create a negative charge that balances the positive charge of the protons in the atomic
nucleus
Valence Electrons

 Each element from Groups 1 to 8 have electron(s) on their outermost shell. These electrons are called
valence electrons.

 The number of electrons is determined by their group number (i.e., Group 1 elements have one
electron, group 2 have 2, and so on, until 8)

 Of these groups, only group 8 elements are non-reactive under normal circumstances,while the rest are
reactive

Valence Electrons and the Octet Rule

 Why are noble gases generally non-reactive under normal circumstances?

-Because they have a stable electron configuration; that is, the number of electrons on their valence shell
is at full capacity which is 8.

 When elements have a full number of electrons in

their valence shell, they have satisfied the octet rule.

-In the formation of a chemical bond, these electrons

are either shared or transferred to satisfy this rule:
main-group elements tend to bond in such a way that
each atom has eight electrons in its valence shell,
making its electron configuration the same as that of
noble gases.

Lewis Theory, the Octet Rule, and Atomic

Bonding

 Lewis Theory: a structural depiction that obeys the octet rule and, using a set of rules that takes into
account the number of electrons to satisfy the octet rule (N) and the number of electrons available, is
used to predict the number of electrons to be shared.

Elements of the theory:

 Valence electrons play a fundamental role in chemical bonding.

 Ionic bonding involves the transfer of one or more electrons from one atom to another.

 Covalent bonding involves sharing electrons between atoms.

 Electrons are transferred or shared such that each atom gains an electron configuration of a noble gas
(ns2np6 ),i.e. having 8 outer shell (valence) electrons.

 This arrangement is called the octet rule.

 Exceptions to the octet rule do exist and will be explored later.

Lewis Theory, the Octet Rule, and Atomic Bonding

 Lewis Symbols represent the resulting structures that accommodate the octet rule. In a Lewis symbol,
an element is surrounded by up to 8 dots, where elemental symbol represents the nucleus and the
dotsrepresent the valence electrons.

 Ionic Bonding results when an electron or electrons are transferred from one atom to another. The
transfer results in each attaining an octet or Noble gas electron configuration.

 Covalent chemical bonds involve the sharing of a pair of valence electrons by two atoms, in contrast to
the transfer of electrons in ionic bonds.

 Covalent bonds lead to stable molecules if they share electrons in such a way as to create a noble gas
configuration (octet:ns2np6) for each atom.
Lone Pairs

 Since hydrogen has only one electron in its valence, it satisfies the octet rule with a duet.

 When other covalent species form, there are additional electron pairs that do not. participate in
bonding. These are called “lone pairs” (lp)

Multiple bonds

 The oxygen and nitrogenthat makes up the bulk of the atmosphere also exhibits covalent bonding in
forming diatomic molecules.

Polyatomic Molecules (More than two atoms)

 Carbon dioxide: CO2

Molecular Structure and Properties

 Properties of molecular substances depend on the structure of the molecule.

 Structure include many factors

- Arrangement of the atoms

- Type of bonding between atoms (ionic, polar covalent, covalent)

- Shape of the molecule

 Valene Shell Electron Pair Repulsion Theory (VSEPR Theory) allow us to predict shapes of molecules
based on molecular geometry (orientation of atoms in space)
Lewis Theory and Electron Groups

 Lewis theory also predicts there are regions of electrons in an atom.

-Some regions result from placing shared pairs of valence electrons between bonding nuclei

-Other regions result from placing unshared valence electrons on a single nuclei.

 Lewis theory: regions of electron groups should repel each other, because they are regions of negative
charge

-Can be extended to predict the shapes of the molecules

-The position of atoms surrounding a central atom will be determined by where the bonding electron
groups are.

-The positions of the electron groups will be determined by trying to minimize repulsions between them.

 The Lewis structure predicts the number of valence electron pairs around the central atom(s).

 Each lone pair of electrons constitutes one electron group on a central atom.

 Each bond constitutes one electron group on a central atom, regardless of whether it is single, double,
or triple.

Two Electron Groups: Linear Geometry

 When there are two electron groups around the central atom, they will occupy positions on opposite
sides of the central atom.

 This results in the electron groups taking a linear geometry.

 The bond angle is 180°

Three Electron Groups: Trigonal Planar Geometry

 When there are three electron groups around the central atom, they will occupy positions in the shape
of a triangle around the central atom.

 This results in the electron groups taking a trigonal

planar geometry.

 The bond angle is 120°.

Four Electron Groups: Tetrahedral Electron Geometry

 When there are four electron groups around the central atom, they will occupy positions in the shape of
a tetrahedron around the central atom.

 This results in the electron groups taking a tetrahedral

geometry.

 The bond angle is 109.5°

Five Electron Groups: Trigonal Bipyramidal

 When there are five electron groups around thecentral atom, they will occupy positions in the shape of
two tetrahedral that are base to base with the central atom in the center of the shared bases.

 This results in the electron groups taking a trigonal bi-

pyramidal geometry.

 The positions above and below the central atom are called
the axial positions.

 The positions in the same base plane as the central atom

are called the equatorial positions. The bond angle between
equatorial positions is 120°.

 The bond angle between axial and equatorial positions is

90°

Six Electron Groups: Octahedral Electron Geometry

 When there are six electron groups around the central atom, they will occupy positions in the shape of
two square–base pyramids that are base–to–base with the central atom in the center of the shared bases.

 This results in the electron groups taking an octahedral geometry. It is called octahedral because the
geometric figure has eight sides.

 All positions are equivalent.

 The bond angle is 90°.

Not Quite Perfect Geometry

 The actual geometry of the molecule may be different from the electron geometry.

 When the electron groups are attached to atoms of different size, or when the bonding to one atom is
different than the bonding to another, this will affect the molecular geometry around the central atom.

 Lone pairs also affect the molecular geometry. They occupy space on the central atom but are not
“seen” as points on the molecular geometry.

Because the bonds

and atom sizes are

not identical in

formaldehyde, the

observed angles are

slightly different from

ideal.

Effects of Lone Pair

 Lone pair groups “occupy more space” on the central atom because their electron density is exclusively
on the central atom, rather than shared like bonding electron groups.

 Relative sizes of repulsive force interactions is as follows:

--Lone Pair – Lone Pair > Lone Pair – Bonding Pair > Bonding Pair – Bonding Pair

 This affects the bond angles, making the bonding pair angles smaller than expected.
Electron Configuration and Valence Bond Theory

Electrons: The Key to Chemical Reactions

Electron Configuration

 Atomic orbitals: regions in the atom where electrons are most likely found.

 Each atomic orbital has four subshells in which there are four types: s, p, d, f. Each subshell can only
accommodate a number of electrons.

-S = 2, p = 6. d = 10. f = 14

 The distribution of electrons inthese orbitals

is known as electron configuration.
Electron Configuration

 Remember: s= 2e, p = 6e, d = 10e, f =14e

-The electrons are even because they come in

identical pairs. Therefore, there is an odd
number of subshells per atomic orbital.

 The electron configuration can be written by

noting the atomic orbital (a number), followed by
the subshell (s, p, d, or f), and filling these
subshells with the total amount of electrons of
that element.

Electron Configuration and Valence Bond Theory

 Principles of quantum mechanics were applied by Linus Pauling to molecules.

 They reasoned that bonds between atoms would occur when the orbitals on those atoms
interacted to make a bond.

 The kind of interaction depends on whether the orbitals align along the axis between the
nuclei, or outside the axis.

 Describes how atomic orbitals

form bonds

 A covalent bond is formed by the

overlapping of two half-filled atomic
orbitals of two atoms having
electrons with opposite spin.
Valence Bond Theory

 In the formation of a bond,

simple atomic orbitals on the
central atom “mix” to form new
“hybrid” orbitals. This process is
known as orbital hybridization.

 Take note: hybridization

happens only on the participating
orbital.

Valence Bond Theory: Main Concepts

1. The valence electrons of the atoms in a molecule reside in quantum- mechanical atomic orbitals.
The orbitals can be the standard s, p, d, and f orbitals, or they may be hybrid combinations of
these.
2. A chemical bond results when these atomic orbitals interact and there is a total of two electrons in
the new molecular orbital
a. The electrons must be spin paired.

3. The shape of the molecule is determined by the geometry of the interacting orbitals.

Orbital hybridization: sp3 hybridization

 Atom with four electron groups around it

 Tetrahedral geometry –109.5°angles between hybrid

orbitals

 Atom uses hybrid orbitals for all bonds and lone pairs

 Single bonds formed are known as sigma bonds (σ

bonds)

Orbital hybridization: sp3 hybridization

 The four valence orbitals of

the carbon and nitrogen combine mathematically to form our equivalent hybrid orbitals

- Called sp3 orbitals because it is made up of one s orbital and three p orbitals

 Each of the four valence electrons on the carbon occupies a single sp3 orbital
Orbital hybridization: sp2 hybridization

 Molecule with three electron groups around it

 Trigonal planar system

o C = trigonal planar
o N = trigonal bent
o = linear

 120°degree bond angles, flat

 Contains double bonds, in which one bond is a sigma bond, while the other is a pi (π) bond

Orbital hybridization: sp2 hybridization

 Three atomic orbitals on each central molecule (2s, 2px, 2py) combine, leaving one orbital
unhybridized.

 The carbon-carbon bond forms a sigma bond, while the side-by-side overlap of the two unhybridized
orbitals form the pi bond.

Orbital hybridization: sp hybridization

 Atom with two electron groups

 Linear in shape, 180° bond angle

 Contains triple bond: one sigma, and two pi bonds.

Why try to understand these concepts?

 Organic compounds have covalent bonds.

 To understand how organic reactions work, it is important to understand how covalent bonds form.

 All the preceding theories allows one to better understand the nature of organic reactions and their
properties.

So, why is Carbon central to Organic

Chemistry?

Why Carbon?

 Carbon, together with H, is present in all organic

compounds.

 Carbon is tetravalent.

 Carbon bond is not randomly oriented; they form

tetrahedron.

 Carbon can bond to one another to form extended chains; chains can double back to form rings

Why Carbon?

 Carbon, together with H, is present in all organic compounds.

 Carbon is tetravalent.

 Carbon bond is not randomly oriented; they form tetrahedron.

 Carbon bond is not randomly oriented;they form tetrahedron.

Why Carbon?

 Carbon, together with H, is present in all organic compounds.

 Carbon is tetravalent.

 Carbon bond is not randomly oriented; they form tetrahedron.

 Carbon can bond to one another to form extended chains;

chains can double back to form rings

Why Carbon?
 Carbon, together with H, is present in all organic compounds.

 Carbon is tetravalent.

 Carbon bond is not randomly oriented; they form tetrahedron.

Basic Chemical Reactions