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2c_p_ovelap_resonance_post

2c_p_ovelap_resonance_post

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Published by: api-3767370 on Oct 16, 2008
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05/09/2014

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Sec. 4 - Resonance
1
\u03c0Bond Overlap and Resonance
Lets exam\u03c0 overlap with the conjugated system butadiene, CH2=CHCH=CH2
1.34 \u00c5
CH3
H3C
\u03c3(sp3 - sp3)
1.54 \u00c5
CH
H2C
CH3
1.50 \u00c5
CH
H2C
CH
CH2
1.47 \u00c5
C
HC
C
CH
C
HC
CH
CH2
C
HC
CH3
1.46 \u00c5
1.43 \u00c5
1.37 \u00c5
\u03c3(sp - sp3)
\u03c3(sp - sp2)
\u03c3(sp \u2013 sp)
Why does the bond length between the carbon-carbon single bonds become smaller
as the hybridization changes from sp3 to sp?
Conjugation: systems that have a p orbital on an atom adjacent to a double bond
\u2013 molecules with delocalized\u03c0 bonds \u2013 are called conjugate unsaturated systems

saturated
unsaturated
conjugated and unsaturated

1.20 \u00c5
H2C
CH2
\u03c3(sp2 - sp2), \u03c0(p-p)
HC
CH
\u03c3,(sp \u2013 sp), \u03c0(p-p)
\u03c3(sp2 - sp3)
\u03c3(sp2 - sp2)
Because the sp3 orbitals have more p character and are longer. The more s character the orbital has
the smaller and shorter it is. Sp3(1/4 s, \u00be p) \u2013 sp2 (1/3s, 2/3 p) \u2013 sp (1/2 s, \u00bd p)
Sec. 4 - Resonance
2
What effect does conjugation have of the stability of the molecule?
HydrogenationH2/Ni
H2/Ni
\u2206H = -30.3 kcal/mol
We would assume\u2206H = 2 x - 30.3 kcal/mol
= - 60.6 kcal/mol
Observed
\u2206H = - 57.1 kcal/mol
For an exothermic reaction the more heat given off the less stable the molecule is
PotentialEn
ergy
Reaction Coordinate
C
H3
CH3
C
H2
CH2
\u2206Hcalc= - 60.6 kJ/mol
\u2206Hobs= - 57.1 kJ/mol
More stable than
calculated
Sec. 4 - Resonance
3
Conclusion:Two conjugated bonds are not utterly unconnected.
There is some overlap of adjacent\u03c0 electrons which shortens the C2 \u2013C3
bond and helps stabilize the molecule. Although, this overlap is small
What is causing the overlap of adjacent\u03c0 electrons
Lets look at resonance structures
C
C
C
C
H
H
H
H
H
H
C
C
C
C
H
H
H
H
H
H
C
C
C
C
H
H
H
H
H
H
C
C
C
C
H
H
H
H
H
H
+
+
Best resonance form shows alternating double and single bonds. But some
double bond character is possible between carbons 2 and 3.

most stable
resonance
form

1
2
3
4

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