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Topic: Resonance in conjugated Alkynes  (Read 3179 times)

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Offline AdiDex

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Resonance in conjugated Alkynes
« on: March 08, 2017, 04:39:27 AM »
I've never seen any example of Resonance in conjugated Alkynes. Does Resonance exist in C≡C system?
For example
  .

Or
 
Diacetylene

It is certain that -CN group is a -M group but what about -C≡CH? Is the Bond length between C2 and C3 shorter as compared to typical C-C bond?
« Last Edit: March 08, 2017, 05:22:15 AM by AdiDex »

Offline Corribus

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Re: Resonance in conjugated Alkynes
« Reply #1 on: March 08, 2017, 09:45:33 AM »
Resonance exists, but it tends to be more complicated due to more dramatic bond alternation in conjugated oligo-acetylenes. You get cumulenic (charge transfer) forms as well.
What men are poets who can speak of Jupiter if he were like a man, but if he is an immense spinning sphere of methane and ammonia must be silent?  - Richard P. Feynman

Offline AdiDex

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Re: Resonance in conjugated Alkynes
« Reply #2 on: March 09, 2017, 04:52:46 AM »
Can you please tell me any book or any Link ,where I can read more about it ? What do you mean by "dramatic bond alternation" ?

Offline Corribus

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Re: Resonance in conjugated Alkynes
« Reply #3 on: March 09, 2017, 09:34:20 AM »
Basically, triple bonds are shorter than single bonds. For a true resonance structure, all the bonds should be equal in length. For long (like, infinite) chains of alternating triple and single bonds, the alternated form is lower energy. This symmetry breaking is called a Peirels distortion (https://en.wikipedia.org/wiki/Peierls_transition) and is common in conjugated polymers. It is a reason there is an optical bandgap in polyacetylene (conjugated polymers are semiconductors rather than conductors, basically). Anyway, the energy difference between the bond alternated form and the unalternated resonance form limits the degree of conjugation/resonance (whatever you want to call it) as the number of sequential ethynes increases.
What men are poets who can speak of Jupiter if he were like a man, but if he is an immense spinning sphere of methane and ammonia must be silent?  - Richard P. Feynman

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