CH1102 Molecular Structure

CE1102 Molecular Structure for

Engineers

Lecture 7
Dr A J Sutherland
2.3 Resonance effect
•Neither resonance form is correct on its own
•True structure is an intermediate between the two
resonance forms – called a resonance hybrid.

oved by measurements - typical C—O = 1.35 Å

C O = 1.20 Å
acetate find both bonds = 1.27 Å
2.3 Resonance effect
•Resonance only involves location of non-bonding
electrons and π electrons
•Atoms DO NOT move
•Resonance effective over far greater distances
than inductive effect

More evidence
benzene

All six C-C BUT NEVER

bonds the same
∴ hybrid DRAW LIKE
length THIS ALWAYS
2.3 Resonance effect
Also nitro group ..

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arged intermediates
rst though what is an intermediate?

http://www.sparknotes.com/chemistry/ http://usm.maine.edu/~newton/Chy251_253/
kinetics/mechanisms/section1.rhtml Lectures/Reactions/ReactionProfiles.ht
2.3 Resonance effect
ntermediates can be cations, e.g.

ow go from one to the other?

empty p orbital  vacant p orbital perfectly aligned with two
where positive p orbitals forming the π bond – electron
charge is pair then moves

positive charge appears to move but in reality only electrons

2.3 Resonance effect
Arrow pushing

• represents movement of a pair of electrons

•in resonance these are π electrons or non-bonding electro
•arrow starts where electron pair is originally on left han
structure and points to where the electron pair ends up
right hand structure
i.e. arrows show how one resonance form turns into the oth
2.3 Resonance effect
Examples
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2.3 Resonance effect
More examples

effectively can
move positive and
negative charges
but remember it is
only electron
pairs that actually
move
Can involve more than one bond

can do more than one

arrow at a time but take
care…
2.3 Resonance effect
More examples

benzylic cation

Note the positions

of the double
bonds in the
benzene ring
2.3 Resonance effect
benzylic anion

Again note the

positions of
the double
bonds in the
benzene ring

Notes
• ∴
means instant movement αλ λ ατ ο µ σ σ τ αψ
σ τ ι λ λ , ο ν λ ψ ε λ ε χ τ ρ ο ν π αι ρ σ µ ο ϖε
• α ρ ρ ο ωσ αλ ωαψσ στ αρ τ ατ αν ε λ ε χ τ ρ ο ν
π α ι ρ ε ι τ η ε ρ ο ν αν ατ ο µ ο ρ ι ν τ ηε µ ι δ δ λ ε
ο φ α β ο ν δ
• ι φ τ ηε αρ ρ ο ω στ αρ τ σ φ ρ ο µ α β ο ν δ τ η ε
β ο ν δ β ρ ε ακ σ
2.3 Resonance effect
Rules for resonance
1.Resonance forms are imaginary, not real. The real
structure lies somewhere in between the resonance forms.
The real molecule has a single unchanging structure.
It does not switch back and forward between different
limiting structures.
2.Resonance forms differ only in the distribution of their
π and non-bonding electrons. Positions of all atoms do
not change from one form to another.
5.Different resonance forms do not have to be equivalent,
actual structure will be closest to most stable
resonance form.

strong base

minor majo
r
negative charge more stable on O than C
2.3 Resonance effect
Rules for resonance
4.The greater number of resonance forms and the more
similar they are the greater the resonance
stabilisation.
more stable than

5.Resonance forms must obey normal valency rules.

6.
7.
8.
9.
11.The resonance hybrid (i.e. the real structure) always
more stable than any individual form.