STRUCTURAL EFFECTS Gladys I. Bathan
Dec 13, 2015
I. RESONANCE
A molecule’s structure can have several forms that differ only in the placement of electrons
I. RESONANCE
Structural forms are called contributing structures or resonance structures or canonical structures
I. RESONANCE
TRUE STRUCTURE - Hybrid of all contributing or resonance structures
http://www.masterorganicchemistry.com/2011/11/30/introduction-to-resonance-2-curved-arrows/
I. RESONANCE
How to show the movement of electrons?
http://www.masterorganicchemistry.com/2011/11/30/introduction-to-resonance-2-curved-arrows/
I. RESONANCE
Allowed movement of electrons
bond lone pair
lone pair bond
bond bond* Only p bonds are broken or formed
I. RESONANCE
bond lone pair
http://www.masterorganicchemistry.com/2011/11/30/introduction-to-resonance-2-curved-arrows/
I. RESONANCE
lone pair bond
http://www.masterorganicchemistry.com/2011/11/30/introduction-to-resonance-2-curved-arrows/
I. RESONANCE
bond bond
http://www.masterorganicchemistry.com/2011/11/30/introduction-to-resonance-2-curved-arrows/
I. RESONANCE
Types of electron delocalization
A. - electron delocalization
B. lone pair delocalization
C. σ electron delocalization
(C-H hyperconjugation)
A. - electron delocalization
p Electrons - electrons found in api bond
- electron delocalization is observed in compounds containing conjugated double or triple bonds.
B. lone pair delocalization
Allylic lone pairs (Atom with lone pair next to a pi bond)
Klein, Organic Chemistry 2e
C. Hyperconjugation
Electron delocalization involving sigma bonds (C-C, C-H) and pi bonds.
More canonical structures lead to better stability of the molecule
I. RESONANCE
Molecules with resonance structures meet the ff criteria:
Criterion 1: Have at least one pi bond.
Criterion 2: Have at least one of the following
a) a second, conjugated pi bond, or
b) an allylic or α-atom with at least one lone
pair of electrons, or
c) an allylic atom with a vacant p-orbital.
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf
Identifying structures with resonance
1. Does the molecule have at least
one pi bond?
YES : a. number the two atoms of
the pi bond “1” and “2”
b. go to step 2.
NO : molecule does not have
resonance. http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf
Identifying structures with resonance
2. Circle the atom(s) directly bonded
to atom “1”.
3. Circle the atom(s) directly bonded
to atom “2”.
4. Label the circled atoms “3”, “4”,
“5”, and “6”.
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf
Identifying structures with resonance
5. Is atom 3, 4, 5 or 6 part of another pi bond?
YES : molecule has resonance
NO : Go to step 6.
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf
Identifying structures with resonance
6. Does atom 3, 4, 5 or 6 have at
least one lone pair of electrons
or a single unpaired electron?
YES : the molecule has resonance
NO : Go to step 7.
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf
Identifying structures with resonance
7. Does atom “3, 4, 5 or 6 have a
vacant p-orbital (usually a
carbocation)?
YES : molecule has resonance
NO : molecule has no resonance
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf
Identifying structures with resonance
7. Does atom “3, 4, 5 or 6 have a
vacant p-orbital (usually a
carbocation)?
YES : molecule has resonance
NO : molecule has no resonance
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf
II. INDUCTIVE EFFECT
Electronic effects of an atom or functional group contributed through single bonds
Factors: electronegativity, position within the structure
II. INDUCTIVE EFFECT
Inductive effect weakens with increasing distance from the substituent
Inductive effect weakens with decreasing electronegativity of the substituent
II. INDUCTIVE EFFECT
A substituent may WITHDRAW or RELEASE electrons
ELECTRON-WITHDRAWING SUBSTITUENT
-helps to offset negative chargeELECTRON-RELEASING
SUBSTITUENT
-helps to offset the positive charge
Electron attracting/withdrawing inductive effect with excess positive charges
N+
RR
R
+NH3
+NO2
those with electronegative atoms
NH2 OH OCH3
F
ClBr
groups exhibiting orbital electronegativity
C N N N
those with easily polarizable valence electrons
I-
Electron releasing/donating inductive effect alkyl groups
CH3
negative groups
COO-
S-
O-
H3C CO
O
-- H3C S-
CHH3C
H3CC N
R CO
OC
O
OO SR
O
O
O
III. STERIC EFFECT
http://www.utdallas.edu/~scortes/ochem/OChem1_Lecture/Class_Materials/08_conform_anal.pdf
Most stable conformation has the least Van der Waals repulsion