Reactivity in Chemistry

Carbonyl Addition

CO7. The Mechanism of Carbonyl Addition: Step One

   

Carbonyls act most importantly as electrophiles. They attract a pair of electrons from a nucleophile. When that happens, a bond forms between the nucleophile and the carbonyl carbon.

At the same time, the carbon-oxygen bond breaks. We think of that as a consequence of donating a pair of electrons into the LUMO of the carbonyl. The LUMO on the carbonyl is the C-O pi antibonding orbital. When that orbital is populated, there is no longer a net lowering in energy due to the pi interaction between the carbon and oxygen. The pi bond breaks. The electron pair from the pi bond goes to the oxygen, the more electronegative of the two atoms in the original bond. It becomes a lone pair.

 

After the pi bond breaks, the reaction reaches a branching point or decision point. The reaction may go forwards or backwards.  In other words, this reaction can occur in equilibrium.

Figure CO7.1. Nucleophilic additions can be reversible.

 

To go backwards, the reaction simply slides into reverse. A lone pair on the oxygen donates to the carbon, forming a pi bond again, and pushes the nucleophile off. Whether the reaction ends up going forward or sliding backward depends partly on the relative stability of those two ends of the reaction. That's often very difficult to assess qualitatively, because there are too many factors involved. However, one factor that plays a role is charge stability. Because an "O minus" or alkoxide is produced in this reaction, if the original nucleophile was a more reactive ion than an alkoxide, the reaction probably goes to the right.

For that reason, many of the best nucleophiles for these reactions involve carbon anions or hydrogen anions.  Those anions are less stable than oxygen anions.

Figure CO7.2. Anion stability is a factor in the equilibrium shifting right.

 

If the nucleophile were less reactive than alkoxide, the reaction could easily go to the left again.  For that reason, stable halide ions (fluorides, chlorides, bromides, iodides) are not very good nucleophiles for these reactions.  They have lone pairs, they even have negative charges, but the anion that would be produced would generally be less stable than the original halide ion.

Figure CO7.3. Anion stability is a factor in the equilibrium shifting left.

 

Problem CO7.1.

Provide curved arrows and predict the direction of equilibrium in the following cases.

What happens after the initial equilibrium? In most cases, the alkoxide that is formed will become protonated. It will pick up a proton to become an alcohol. The source of the proton may be an acid, deliberately added to provide the H+. Alternatively, it may just be a very slightly acidic molecule such as water or another alcohol.

 

This site was written by Chris P. Schaller, Ph.D., College of Saint Benedict / Saint John's University (retired) with other authors as noted on individual pages.  It is freely available for educational use.

Creative Commons License
Structure & Reactivity in Organic, Biological and Inorganic Chemistry by Chris Schaller is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported License

Send corrections to cschaller@csbsju.edu

 

This material is based upon work supported by the National Science Foundation under Grant No. 1043566.

Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation.

 

Navigation:

Back to Carbonyl Addition Index

Back to Reactivity

Back to Web Materials on Structure & Reactivity in Chemistry