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Meaning of Organic?
Later Justus von Liebig, a noted 19th century chemist, declared the synthesis of urea
the very first beginning of the actual scientific organic chemistry
diamond
carbon nanotube
Carbon can form strong bonds with not only carbon but with other elements
(e.g. hydrogen, nitrogen, oxygen, halogens)
Depending upon the order of the bond connections (both constitution and configuration)
millions of compounds, all with potentially different properties, can be prepared
Understanding Organic Chemistry is Learning about Bonding and the location of Electrons
H
H
Shorthand drawing
H H
H
H
H H
3-dimensional
drawing
wedge and dash
lines have meaning
Organic chemistry is fundamentally about what electrons do, and how they behave
During a reaction old bonds are broken and new bonds form
Therefore, if we know more about the electrons we can understand organic chemistry
Background of an atom
The number of protons determines the element (also is the atomic number)
Carbon therefore has 6 protons located in the nucleus
Usually the nucleus also contains an identical number of neutrons as protons
If the number is different it is called an isotope
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
2
3
4
s
s,p
s,p,d
s,p,d,f
s
p
d
f
1
3
5
7
Organic chemistry is primarily concerned with only the first two shells
(therefore only the s and p atomic orbitals)
Also due to only two spin states for an electron
Only two electrons can be placed in each orbital
(Pauli exclusion principle)
Orbitals are filled by electrons starting in the lowest energy orbital
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
Bonding
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
Type of Bonds
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
Consider F2 (fluorine gas)
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
Other representations
Polar Bonds
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
Electronegativity Tables
Linus Pauling established values to associate with each element
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)
Formal Charges
A formal charge represents a full charge on the atom
(assuming no polarity of the covalent bond)
To calculate:
Formal charge = (group number) (nonbonded electrons) (shared electrons)
Use group numbers, not atomic numbers!
Consider ammonium:
Acid/Base Reactions
Important considerations for Organic chemistry:
What makes a compound acidic?
How do we determine acid strengths?
Need to first consider what definition of acid/base reactions we are using
Arrhenius definition:
Acids something that dissociates in water to give hydronium ion (H3O+)
Bases something that dissociates in water to give hydroxide ion (HO-)
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 Brnsted-Lowry definition
Other compounds, however, would not be considered bases
under Arrhenius which do qualify with Brnsted-Lowry
base
Cl
acid
H 2O
conjugate
acid
H3O
Cl
conjugate
base
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
base
Cl
H3O
Cl
acid
This definition is far more general, but any acid or base in Brnsted/Lowry definition
remains the same in the Lewis definition
Introduces new terms that are used in many organic reactions
A Lewis base is called a nucleophile - lover of nuclei
A Lewis acid is called an electrophile - lover of electrons
increasing
generality
Acid
Base
Lavoisier
(1789)
oxidized
substance
substance to
be oxidized
Arrhenius
(1887)
H+ source
HO- source
Brnsted/Lowry
(1923)
H+ donor
H+ acceptor
Lewis
(1923)
e-pair acceptor
electrophile
e-pair donor
nucleophile
unusually
low LUMO
unusually
high HOMO
HOMO-LUMO
(1960s)
Acid-Base Reactions
HO-
H+
HO-H
Acid-Base Reactions
HO-
NH3:
HO-
NH3:
H+
HO-H
Arrhenius
H+
+
NH3-H
Brnsted/Lowry
BH3
-
HO-BH3
Lewis
BH3
+
-
NH3-BH3
Lewis
Acid Strength
Organic acids are defined by the acid dissociation constant (Ka)
Electron withdrawing groups can pull electron density away from another region of molecule
(this through bond effect is called inductive)
The negative charge on the oxygen could be placed on either oxygen using Lewis structures
Rules of Resonance
The negative charge can therefore be delocalized over both oxygen atoms
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
- Amount of Charge
Also related to number of bonds in a structure
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
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
Excess negative charge is located on three carbon atoms, not on all five equally
Have already observed this with acidity difference between ethanol and acetic acid
H3C
H3C N O
H3C
N N O
N N O
4.47 D
1.30 D
H3C CH3
H2C CH2
1.54
1.32
1.39