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What is the effect of changing all the hydrogen atoms in benzene to deuterium? For example, which of the following reactions occurs at a faster rate?

nitration & reduction

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Page 513 of Organic Reaction Mechanisms by Bansal references the work of Melander in Arkiv för Kemi, 2, 211 (1950). This states that the rates of nitration for benzene vs benzene-d6 are about the same, implying that the addition of the nitronium ion is rate controlling and not the weakening of the C-H / C-D bond. However in case of sulphonation H containing benzene reacts faster than D containing benzene.

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  • $\begingroup$ This would imply an early transition state for the nitronium-benzene complex. $\endgroup$ – Lighthart Mar 18 '16 at 1:43
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This is an example of an inverse kinetic isotope effect.

When a transition state increases in coordination then differences gained from vibrational bending energy for the $\ce{C-D}$ vs $\ce{C-H}$ bond favor $\ce{C-D}$, lowering the transition state energy relative to starting materials, and increasing reaction rate.

In this case, the intermediate is the protonated benzene changing a reaction center from $\mathrm{sp^2}$ to $\mathrm{sp^3}$, increasing coordination.

The perdeuterated benzene will react faster. The effect will probably be on the order of half again as faster.

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  • $\begingroup$ "order of half again as faster.", can you explain it a bit $\endgroup$ – yawar Mar 18 '16 at 6:51
  • $\begingroup$ I would guess the rate constant to be 50% higher. However, Beerhunter's data says my guess is incorrect. $\endgroup$ – Lighthart Mar 18 '16 at 21:20
  • $\begingroup$ I would refer to the book and see what happens $\endgroup$ – yawar Mar 19 '16 at 9:50

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