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  hyperconjugation and resonance : clear solution !!!!   Awaiting Review for Nickels
Tagged with:       [Post New]posted on 18 Apr 2008 22:07:58 IST    
What is Hyperconjugation ?


Hyperconjugation is the stabilising interaction that results from the interaction of the electrons in a s-bond (usually C-H or C-C) with an adjacent empty (or partially filled) p-orbital or a p-orbital to give an extended molecular orbital that increases the stability of the system.
Based on the valence bond model of bonding, hyperconjugation can be described as "double bond - no bond resonance" but it is not what we would "normally" call resonance, though the similarity is shown below.
What is the key difference between hyperconjugation and resonance ?
"hyperconjugation involves a sigma orbital component, resonance is just pi orbitals " 
Hyperconjugation is a factor in explaining why increasing the number of alkyl substituents on a carbocation or radical centre leads to an increase in stability.
 
Let's consider how a methyl group is involved in hyperconjugation with a carbocation centre. 
interaction of a methyl group
First we need to draw it to show the C-H s-bonds.
Note that the empty p orbital associated with the positive charge at the carbocation centre is in the same plane (i.e. coplanar) with one of the C-H s-bonds  (shown in blue.)
look at the sigma bonds
This geometry means the electrons in the s-bond can be stabilised by an interaction with the empty p-orbital of the carbocation centre.
(this diagram shows the similarity with resonance and the structure on the right has the "double bond - no bond" character)
electrons in the sigma bond interact with the empty p orbital
The stabilisation arises because the orbital interaction leads to the electrons being in a lower energy orbital
 

orbital interaction diagram

 

Of course, the C-C s-bond is free to rotate, and as it does so, each of the C-H s-bonds in turn undergoes the stabilising interaction.
So the ethyl cation has 3 C-H s-bonds that can be involved in hyperconjugation.
The more hyperconjuagtion there is, the greater the stabilisation of the system.
So for example, the t-butyl cation has 9 C-H s-bonds that can be involved in hyperconjugation. Hence (CH3)3C+ is more stable than CH3CH2+
The effect is not limited to C-H s-bonds, appropriate C-C s-bonds can also be involved in hyperconjugation.


hope u would have got evrythin clear...........

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coolriya (482)

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Olaaa!! Perrrfect answer. 88  [109 rates]

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The.CHOSEN.ONE is offline comment by The.CHOSEN.ONE    (posted on 18 Apr 2008 22:10:04 IST)
GR8
coolriya
coolriya is offline comment by coolriya    (posted on 18 Apr 2008 22:12:04 IST)
more comments awaited..............
Shesha
Shesha is offline comment by Shesha    (posted on 18 Apr 2008 22:26:10 IST)
nice work!
drritu
drritu is offline comment by drritu    (posted on 13 May 2008 17:30:34 IST)
good work
entropy
entropy is offline comment by entropy    (posted on 21 May 2008 23:00:52 IST)
awesome
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