Organic Chemistry Question

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NarutoMD

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This problem is taken from TBR. TBR states that bond C is stronger than bond A, despite the fact that both have the same sp2-sp3 bond. The only difference between bond C and A is that C has a more substituted sp3 C. But what I initially thought was that bond A would be stronger than bond C since the highly substituted carbon in bond C would result in more electronic repulsion which ultimately makes the bond a little longer and weaker. However, TBR says bond C is stronger because of the substituted carbon. Does anyone have a better explanation for this? Thanks

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This problem is taken from TBR. TBR states that bond C is stronger than bond A, despite the fact that both have the same sp2-sp3 bond. The only difference between bond C and A is that C has a more substituted sp3 C. But what I initially thought was that bond A would be stronger than bond C since the highly substituted carbon in bond C would result in more electronic repulsion which ultimately makes the bond a little longer and weaker. However, TBR says bond C is stronger because of the substituted carbon. Does anyone have a better explanation for this? Thanks

I remember being confused by this too. I hope someone corrects me if I'm wrong, but I think that adjacent carbon branching actually improves bond strength in this case. It has to do with carbon being an "electron donating group". Basically, the adjacent carbons have empty p orbitals which contribute to the adjacent bonds - this is called hyperconjugation. So a tertiary carbon bonded to a tertiary carbon will be stronger than the C-C bond in ethane.
 
Chemists usually talk about bond strength in terms of homolytic bond dissociation (each atom involved in the bond gets one electron back each, regardless of how electronegative it is relative to the other one). So-called bond dissociation energies, or BDEs, are measured homolytically. So that's why the O-H bond of water is around 119 kcal/mol whereas most C-H BDEs are in the 100 kcal/mol or less range. It might surprise you that an O-H bond is stronger than any C-H bond because you know that one can relatively easily deprotonate water whereas deprotonating a non-acidic hydrogen on an alkane is much harder (think ethane to form ethylene). This is because we're talking about homolytic BDEs when we talk about bond strength.

With that in mind, do this thought experiment. You do a homolytic cleavage of bond a and bond c. Which one will more readily cleave? Look at the products. If you break bond a, you get a two highly unstable radicals. If you break bond c, you get one unstable radical and another radical that is relatively stable - remember that tertiary radicals are more stable than secondary radicals are more stable than primary radicals because of the alkyl donating effect. So bond c should more readily cleave. So based on this analysis alone, I would predict bond c to be weaker than bond a.

However, as the above poster pointed out, since this is an allylic case, you can have hyperconjugation effects. If it is indeed the case that c is stronger than a, then it looks like the hyperconjugation effect wins out - but I don't see a way you can come to that conclusion without actually going out and doing the experiment.
 
Thank you for the clarification. That sure clears up the confusion. To @aldol16, so for the MCAT, do you advise to compare bond strength only by BDE since you said it's hard to conclude the hyperconjugation effect without experimentation?
 
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Thank you for the clarification. That sure clears up the confusion. To @aldol16, so for the MCAT, do you advise to compare bond strength only by BDE since you said it's hard to conclude the hyperconjugation effect without experimentation?

It's not hard to conclude whether there can be hyperconjugation - if there are alkyl donating groups alpha to an olefin, there will be hyperconjugation. What's hard here is that hyperconjugation and BDE arguments are in opposition and so one has to do the experiment to see which wins out. In general, you should be able to tell where there's hyperconjugation and where there isn't.
 
It's not hard to conclude whether there can be hyperconjugation - if there are alkyl donating groups alpha to an olefin, there will be hyperconjugation. What's hard here is that hyperconjugation and BDE arguments are in opposition and so one has to do the experiment to see which wins out. In general, you should be able to tell where there's hyperconjugation and where there isn't.

Thanks!
 
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