I have been reading mechanisms recently, and I find that $\ce{-CH3}$ is a $+I$ effect group. I understand the mechanisms that require this, but can someone explain at the molecular level why is $\ce{-CH3}$ a $+I$ effect group?


According to http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch04/ch4-3-2-1.html:

"Hyperconjugation is the stabilising interaction that results from the interaction of the electrons in a σ-bond (usually C-H or C-C) with an adjacent empty or partially filled p-orbital or a π-orbital to give an extended molecular orbital that increases the stability of the system."

How I see "hyperconjugation" is the formation of partial π bonds. Let's say we have a methyl group bonded to a positively-charged carbon atom with a vacant p orbital.

Ideally, it would be best if we could have an atom with a fully-filled p orbital, which is parallel to the p orbital of the this positively-charged carbon atom, to come and interact with this carbon atom. Such an interaction would stabilise the electron-deficient carbon atom. This is essentially the basis of hyperconjugation.

However, in our case, we do not have such an atom with a fully-filled p orbital around. Instead, what we have is a few C-H σ bonds. These C-H bonds are not parallel to the vacant p orbital of the positively-charged carbon atom but they are very close to parallel, around 19.5 degrees away, assuming that the geometry of the methyl group bonded to that positively-charged carbon atom is tetrahedral.

These C-H bonds are thus able to interact with the electron deficient vacant p orbitals of the positively-charged carbon atom, maybe not maximally, but sufficiently. These interactions would be what I would call "partial π bonds" and they stabilise the electron deficiency of the carbon atom. This interaction is also what is known as "hyperconjugation".

enter image description here

*Please note that the illustration is slightly inaccurate because the hydrogen atom would not pop off the methyl group for the formation of a full π bond between the two carbon atoms. This is only illustrated to better show the interaction of the C-H σ bonds with the p orbital of the positively-charged carbon atom.


Your Answer

By clicking “Post Your Answer”, you agree to our terms of service, privacy policy and cookie policy

Not the answer you're looking for? Browse other questions tagged or ask your own question.