why allene is more unstable than alkyne?

2008-09-15 11:52 pm
why allene is more unstable than alkyne?

回答 (1)

2008-09-16 6:52 am
✔ 最佳答案
Allene has three carbons, two C-C pi-bonding and two C-C sigma bonding.

Alkyene has two carbons, two C-C pi-bonding and one C-C sigma bonding.

So, the difference between allene and alkyene is the number of bonding on the carbon atom.

Alkyene is symmetic along the axis of two C-C sigma bonding. In most simplest terms, there is no dipole moment along these two Carbon centers. So, it is less reactive towards nucleophilic attack.

For allene, the center (beta-) carbon atom has two C-C pi-bonding and two C-C sigma bonding; the alpha- and gamma- carbons has one one pi-bonding and one C-C sigma bonding. You can see a dipole developed along the C-C-C axis.

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As both allene and alkyne are electron rich already, the reaction pathway usually goes to electrophilic type. (Also their LUMO is of higher energy, considering the extra-stable HOMO of alkyne; also sp hybidization gives shorter C-C bond length on allene against usual alkene -> ie, stronger p-p bonding in allene than alkene.)

Rule of thumb: Carbon-anion formation is rare, carboncation formation is common

==> So, Electrophilic attack on alpha- and gamma- (ie 1- / 3-) carbons on the allene is favoured. Reactions such as HBr / Br2 give rise to allyl formation, which is knietically stable intermediate, and thus, give rise to a more stable product (rather than stay unreacted).


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