Home > Community > Which conformations of 2,3-dimethylbutane are more stable?
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Kevin Wright

Which conformations of 2,3-dimethylbutane are more stable?

Barry Gehm  Follow

I found a question in Chem 220 - Organic ChemistryProblem Set 2.

The question is such:

Draw Newman projections for the eclipsed and staggered conformations of 2,3-dimethylbutane viewed along the $C_2-C_3$ axis. Calculate the energy of each conformation, both staggered and eclipsed.

Eclipsed (kcal/mol): H/H, 1.0; CH3/H, 1.3; CH3/CH3, 3.0 kcal/mol. Staggered (kcal/mol): H/H, 0; CH3/H, 0; CH3/CH3, 0.9.

Solution given:

enter image description here

This solution seems reasonable,your book might be wrong.

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Eric Bittner  Follow
New link to user16347s answer. More
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Haroon Lakho  Follow
. Problem #6.More
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Ed Williams  Follow
ursula.chem.yale.edu/~chem220/chem220js/PROBSETS/PS13spr/…More
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Alison Adams  Follow

The correct arrangement (from least stable to most stable) is probably: $4 > 2 > 3 \gtrapprox 1$ based on my calculations for the four gas phase rotamers you can see in the figure below.

Energy scan about the CCCC dihedral angle of 2,3-dimethylbutane

Your reasoning for 4 over 2 sounds good, that would also be my point. For the two minima 1 and 3 (with Boltzmann weights of 46%:54% at the highest calc. niveau (red), 33%:66% at the lowest (blue)) you might also be right. But from the really small energy difference I don’t want to argue too much about it.


My calculation methods seem a bit random, but at first I only wanted to make that fast wB97X-D3/def2-TZVP//HF-3c scan and then decided to calculate the bigger one.

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Chris Mansker  Follow

The solution given by user16347 seems logical but is not really the correct solution. According to the answer the anti form is more stable since it has the least energy, this is actually false. Experimentally, the gauche form with 3 gauche interactions ( that is structure with energy 2.7 ) is more stable than the anti form. The reason being that in the anti form the geminal repulsions due to the methyl on adjacent carbon hakes the system more unstable than the gauche interactions. This for this particular molecule the gauche conformer is more stable.

For details into this concept of geminal repulsion, refered Chapter 2 - Strain and Staibilty from the book Physical Organic Chemistry by anslyn doherthy

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