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1-Intro 2 PDF
1-Intro 2 PDF
Meaning of “Organic”?
graphite
diamond
Depending upon the order of the bond connections (both constitution and configuration)
millions of compounds, all with potentially different properties, can be prepared
And the metabolic and other interactions in the body involve organic reactions
Understanding Organic Chemistry is Learning about Bonding and the location of Electrons
O O
O
H H H H
H H H H H H H H
Shorthand drawing
All atoms indicated
3-dimensional
drawing
wedge and dash
lines have meaning
Organic chemistry is fundamentally about what electrons do, and how they ‘behave’
In Organic Chemistry we study how compounds react
During a reaction old bonds are broken and new bonds form
Therefore, if we know more about the electrons we can understand organic chemistry
The number of protons determines the element (also is the atomic number)
Carbon therefore has 6 protons located in the nucleus
For an uncharged 12C atom, there are 6 protons, 6 neutrons and 6 electrons
Therefore the nucleus, which is responsible for ~3600/1 parts of the mass,
only encompasses ~1 x 10-15 part of the volume (remember V = 4/3 πr3)
Electrons
Unlike the protons and neutrons which are in the nucleus (a relatively fixed point)
we cannot say with certainty where an electron is located at a certain time
(Heisenberg uncertainty principle)
What we can say is that ‘on time average’ the electrons are located in orbitals
(regions of space)
*much bigger region than the nucleus
As the number of electrons increase they reside in concentric shells where each shell
contains subshells known as atomic orbitals of different properties and shapes
shell
atomic orbital
1
s
2
s,p
3
s,p,d
4
s,p,d,f
The different types of atomic orbitals have a characteristic number of orbitals
s
1
p
3
d
5
f
7
Organic chemistry is primarily concerned with only the first two shells
(therefore only the s and p atomic orbitals)
Carbon can therefore only have a maximum of 8 electrons in its outer (2nd) shell
4 atomic orbitals (1s and 3p) with 2 electrons per orbital
Electronic Configuration for Carbon through Fluorine
Octet rule – atom is most stable if its outer shell of electrons is filled
Called ‘octet rule’ since second row atoms (which comprise organic compounds)
have 8 electrons in their outer shell
Therefore an atom will give up, accept, or share electrons in order to achieve
a filled outer shell
Since lithium readily loses an electron to leave an atom with a complete outer shell
it is called electropositive
Halogens, on the other hand, readily gain an electron to complete the outer shell
The sharing of electrons can allow both atoms to fill the outer shell
Each fluorine atom needs one electron to fill the outer shell
One atom cannot donate an electron and have both atoms with a filled outer shell
An alternative is to share two electrons (one from each atom) between both atoms
Lithium Fluoride
Forms ionic bond by lithium ‘donating’ an electron to fluorine
Each outer shell is filled, but no electron density between two atoms
Fluorine gas
Forms covalent bond by sharing electrons
Representation of Organic Structures
Lewis Structures
As already shown with F2 each valence electron
is represented by a dot
Lewis Structures
Other representations
All covalent bonds shown so far have been between identical atoms
Even though the electrons are shared, the electrons can be closer, on time average,
to one nucleus than the other
Elements toward the upper righthand of the periodic table are more electronegative
Also can predict the relative electronegativity of two atoms by their relative placement
in the periodic table
H (2.2)
Li (1.0)
Be (1.6)
B (1.8)
C (2.5)
N (3.0)
O (3.4)
F (4.0)
Cl (3.2)
Br (3.0)
I (2.7)
The numbers are a relative indication of how much the electrons
are ‘attracted’ to a certain atom
As the number becomes larger, the electrons are attracted more by that atom
Formal Charges
To calculate:
Consider ammonium:
Arrhenius definition:
Acids – something that dissociates in water to give hydronium ion (H3O+)
Bases – something that dissociates in water to give hydroxide ion (HO-)
The Arrhenius definition is used to determine the strength of an acid
The strength is determined by how easily the molecule dissociates
in water to give a hydronium ion
Kw = [H3O+][HO-] = 1 x 10-14
pH = -log10 [H3O+]
As can be seen from the reaction above, every Arrhenius acid and base
are still considered acids and bases with the Brønsted-Lowry definition
conjugate
base
acid
H Cl H 2O H3O Cl
acid
conjugate
base
Lewis Definition of Acids and Bases
G.N. Lewis postulated that an acid/base reaction need not involve a transfer of a proton
An acid/base reaction can refer to any reaction that involves the formation of new bonds
Lewis acid: a species that accepts a lone pair of electrons to form a new bond
Lewis base: a species that donates a lone pair of electrons to form a new bond
H2O H Cl H3O Cl
base
acid
This definition is far more general, but any acid or base in Brønsted/Lowry definition
remains the same in the Lewis definition
Theory
Acid
Base
Lavoisier
oxidized substance to
(1789)
substance
be oxidized
Arrhenius
H+ source
HO- source
(1887)
increasing
Brønsted/Lowry
H+ donor
H+ acceptor
generality
(1923)
Lewis
e-pair acceptor
e-pair donor
(1923)
“electrophile”
“nucleophile”
HOMO-LUMO
unusually
unusually
(1960’s)
low LUMO
high HOMO
Acid-Base Reactions
HO- H+ HO-H
HO- H+ HO-H
Arrhenius
+
NH3: H+ NH3-H
Brønsted/Lowry
-‐
HO- BH3 HO-BH3
Lewis
+
-‐
NH3: BH3 NH3-BH3
Lewis
pKa = -log Ka
pKa is a constant for a given acid referring to the pH where half of the acid is ionized
pH refers to the concentration of hydronium ions in solution
How to Predict the Relative Strength of Acids
1. Amongst atoms of similar size, the atom with a greater electronegativity
will be a stronger acid
2. Bigger atoms will be stronger acids
This trend usually is relevant when comparing atoms in the same column
(as the atom becomes larger going down a column,
the excess negative charge is more stabilized)
3. Polar bonds near anion source can stabilize negative charge
(inductive effect)
Electron withdrawing groups can pull electron density away from another region of molecule
(this “through bond” effect is called inductive)
4. Resonance can lower electron density on a given atom
What is resonance?
(also called ‘delocalization’)
Look at a nitro group
The negative charge on the oxygen could be placed on either oxygen using Lewis structures
It turns out neither structure is correct, but the charge is delocalized onto both oxygens
- This process of being able to delocalize the charge onto more than one atom is called
resonance
“Rules” of Resonance
The negative charge can therefore be delocalized over both oxygen atoms
Resonance of Acetate Anion
Rotation of Acetate Group
Comparison of Electron Density for Ethoxide versus Acetate anion
The excess negative charge is more stable on the acetate anion that can resonate,
thus the conjugate acid is more acidic
Important to Remember:
Not all resonance structures need to contribute equally
- Placement of charge
While structure with four formal charges shown is a “valid” resonance form, if structure is
dramatically higher in energy then it is practically an irrelevant resonance form
- Octet rule is important
Having all atoms with a filled octet rule is more stable than a resonance form
that only has 6 electrons in one outer shell
Even if this requires a positive formal charge to be placed on a more electronegative atom
Second row atoms are always more stable with a filled outer shell
Curved arrows represent movement of electrons
Excess negative charge is located on three carbon atoms, not on all five equally
Empirical Evidence for Resonance
Have already observed this with acidity difference between ethanol and acetic acid
Observe also with dipole values for compounds with resonance
H3C
N N O N N O
H3C N O
H3C
4.47 D
1.30 D
1.54 Å
1.32 Å