Professional Documents
Culture Documents
CH 02
CH 02
Second Edition
David Klein
Chapter 2
Molecular Representations
Copyright 2015 John Wiley & Sons, Inc. All rights reserved.
Practice with
conceptual
checkpoint 2.11
Copyright 2015 John Wiley & Sons, Inc. All rights
reserved.
2-20
2.7 Resonance
Drawing lines between atoms inadequately
represents covalent bonds in molecules with
resonance
Remember from General Chemistry, what is
resonance?
Consider the allyl carbocation:
How is the bond-line structure inadequate in
representing the allyl carbocations TRUE
structure?
Copyright 2015 John Wiley & Sons, Inc. All rights
reserved.
2-32
2.7 Resonance
Lets look at the hybridization of the carbons
in the allyl carbocation
Calculate the steric number (# of bonds + lone
pairs)
2.7 Resonance
If all of the carbons have unhybridized p
orbitals, they can overlap
2.7 Resonance
From a molecular
orbital point of view,
when the THREE
unhybridized p orbitals
overlap, THREE new
MOs are formed
How many electrons
are in each of the MOs
for the allyl
carbocation?
Copyright 2015 John Wiley & Sons, Inc. All rights
reserved.
2-35
2.7 Resonance
The allyl carbocation
has a charge of +1.
Which MO is the
missing electron
missing from?
2.7 Resonance
How do we represent the complete picture of
the allyl carbocation provided by valence
orbital and MO theories using a bond-line
structure?
The pi electrons can exist on both sides of the
molecule, so we can use two resonance
contributors to represent the structure
2.7 Resonance
Because neither of the contributors exists
(look at MOs), the average or hybrid is much
more appropriate
vs.
+
+
two contributors
resonance hybrid
How is a resonance arrow different from
equilibrium?
Analogy: a nectarine is a hybrid formed by
Copyright 2015 John Wiley & Sons, Inc. All rights
reserved.
2-38
2.7 Resonance
Resonance makes a molecule MORE stable
Delocalization of electrons
Electrons exist in orbitals that span a greater
distance giving the electrons more freedom
minimizing repulsions
Electrons spend time close to multiple nuclei all at
once maximizing attractions
Delocalization of charge
The charge is spread out over more than one
atom. The resulting partial charges are more
stable than a full +1 charge.
+
Copyright 2015 John Wiley & Sons, Inc. All rights
reserved.
2-39
+
Klein, Organic Chemistry 2e
2.11 Stability of
Contributors
Copyright 2015 John Wiley & Sons, Inc. All rights reserved.
2.11 Stability of
Contributors
How do we assess the stability of resonance
contributors?
1. Formal charge generally DECREASES stability,
especially a +1 charge on an electronegative
atom or -1 on a low electronegativity atom
2. COMPLETE OCTETS INCREASE stability
2.11 Stability of
Contributors
1. Formal charge generally DECREASES stability
2. A +1 charge on an electronegative atom or -1 on
a low electronegativity atom is especially
unstable
3. COMPLETE OCTETS INCREASE stability
2.11 Stability of
Contributors
1. Formal charge generally DECREASES stability
2. A +1 charge on an electronegative atom or -1 on
a low electronegativity atom is especially
unstable
3. COMPLETE OCTETS INCREASE stability
2.11 Stability of
Contributors
The octet rule is usually a bigger factor than
Copyright 2015 John Wiley & Sons, Inc. All rights reserved.
Klein, Organic
Chemistry 2e
3
To be delocalized,
all three atoms
involved MUST have
p orbitals
2-65
overlapping
Copyright 2015 John Wiley & Sons, Inc. All rights reserved.
Cl2CH(CH2)5CO2H