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Lance Chambers

Explanation for bond lengths in trans-hexatriene

Christopher Proescher  Follow

If you derive the π-type molecular orbitals of hexatriene, the three lower-energy MOs which are filled would look something like this (image from p 33 of Fleming's Molecular Orbitals and Organic Chemical Reactions, Reference Edition):

Filled π MOs of hexatriene

I suspect what Clayden is getting at is that in the second MO, there is some antibonding character between C3 and C4, whereas the C1/C2 and C5/C6 interaction is purely bonding.

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History of Computing  Follow
Yes, pretty much. So it is something like a 1.99-bond, if that makes any sense. (That numbers made up, of course.)More
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Joshua Engel  Follow
And this antibonding interaction between C3 and C4 would cause the double bond to have slight single bond character, which would explain the longer than usual bond length for the C3=C4 bond?More
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Eric Weatherby  Follow
You do not have to make it up. You can work out net pi bonding in each linkage by multiplying the coefficients on each pair of bonded atoms, doubling, and adding up the results for all orbital. This gives 0.87 pi bond between C-1 and C-2, 0.48 between C-2 and C-3, and 0.78 between C-3 and C-4. Other bonds are determined by symmetry.More
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