The stability order of alkyl substituted alkenes with respect to heat of hydrogenation was given as

$$\ce{R_2C=CH2} > \ce{RHC=CHR}~(\textit{trans}) > \ce{RHC=CHR}~(\textit{cis}).$$

While I understand that trans alkene is generally more stable than cis, I don't understand why $\ce{R_2C=CH2}$ is the most stable. Shouldn't there be repulsion between the bulky alkyl groups which leads to decrease in stability?


Following is an image of hyperconjugative effect. We can see a $\ce{\sigma}$-orbital delocalising electron pair with an empty $\ce{\pi^\ast}$-orbital.

hyperconjugation movement

The explanation to your problem can be given by deciding whether the effect is "centralized" or "decentralized". Let me explain it by an example.

A quick scene:

Suppose, you and your friend is sitting across a boat ($\ce{C_{you}=C_{friend}}$) in the middle of a river, and both of you have to reach on either bank soon (a process similar to delocalization, probably). Assume the methyl groups to be oars you need to move across the river.

In $\ce{R2C_{you}=C_{friend}H2}$, both the oars are with you. So, only you can row the boat and hence both of you can reach to the bank soon. Technically, the $\ce{\beta-H}$'s are at one carbon, so the effect can happen only on it, hence "centralized" and super-fast.

But, in $\ce{RHC_{you}=C_{friend}HR}$, both of you have the oars. So, both of you can row the boat and therefore both of you will reach to either bank a bit later. Technically, the $\ce{\beta-H}$'s are distributed equally among the carbons, so the effect can happen on either side, hence "decentralized" and not as fast as in the previous case.

As per your concern on steric factors, you may know that "alkyl" is referred to a straight hydrocarbon chain, and it isn't as bulky as to create "steric hindrance".

I guess that makes some sense :)

EDIT: The above stuffs explains how is first isomer the most stable. I'd previously said that "steric effects" doesn't matter, but in case of cis and trans isomers, it matters and it's the only thing that differentiate them (along with polarity). Due to this, cis isomer is least stable among the three.

Reference table of $\ce{\Delta H^°_f}$: http://ursula.chem.yale.edu/~chem220/chem220js/STUDYAIDS/thermo/heats-formation.html#Alkenes (in #C = 4)

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    $\begingroup$ Interesting analogy. I'm wondering whether it was a reflection of the wolf, goat and cabbage problem:) $\endgroup$ – andselisk Jul 12 at 12:59
  • $\begingroup$ Is this a way of saying that in the trans case, the C-H bonds are effectively competing over hyperconjugation, but not in the case with 2 alkyl groups on the same side? $\endgroup$ – Jabbamanga Jul 12 at 15:03
  • $\begingroup$ @Jabbamanga: Not exactly, but it's very similar. Actually, it is a random phenomenon. The orientation of sigma orbital at time of effect decides which C drives the effect. $\endgroup$ – Rahul Verma Jul 12 at 15:14
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    $\begingroup$ @andselisk: ...or the fox, chicken and grain. ;) $\endgroup$ – user55119 Jul 12 at 16:54
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    $\begingroup$ Could you please add thermodynamic considerations of stability. While the analogy is great I would appreciate a more rigorous answer. $\endgroup$ – trinitrotoluene Jul 12 at 18:09

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