Effects of Nucleophile
Effects of Leaving Group
An SN1 reaction speeds up with a good leaving group. This is because the leaving group is involved in the rate-determining step. A good leaving group wants to leave so it breaks the C-Leaving Group bond faster. Once the bond breaks, the carbocation is formed and the faster the carbocation is formed, the faster the nucleophile can come in and the faster the reaction will be completed.
A good leaving group is a weak base because weak bases can hold the charge. They're happy to leave with both electrons and in order for the leaving group to leave, it needs to be able to accept electrons. Strong bases, on the other hand, donate electrons which is why they can't be good leaving groups. As you go from left to right on the periodic table, electron donating ability decreases and thus ability to be a good leaving group increases. Halides are an example of a good leaving group whos leaving-group ability increases as you go down the column.
The two reactions below is the same reaction done with two different leaving groups. One is significantly faster than the other. This is because the better leaving group leaves faster and thus the reaction can proceed faster.
Other examples of good leaving groups are sulfur derivatives such as methyl sulfate ion and other sulfonate ions (See Figure below)
Methyl Sulfate Ion Mesylate Ion Triflate Ion Tosylate Ion
- Uggerud E. "Reactivity trends and stereospecificity in nucleophilic substitution reactions." J. Phys. Org. Chem. 2006; 19; 461-466.
- Vollhardt, K. Peter C., and Neil E. Schore. Organic Chemistry Structure and Function. New York: W. H. Freeman, 2007.
- Petrucci, Ralph H. General Chemistry: Principles and Modern Applications. Upper Saddle River, NJ: Pearson Education, 2007.
- Suggs, William J. Organic Chemistry. Canada: Barron's Educational Series Inc., 2002.
- http://www.youtube.com/watch?v=FuFpjx_ZeT0 (Pretty good summary of SN1 reaction)
1. Put the following leaving groups in order of decreasing leaving group ability
2. Which solvent would an SN1 reaction occur faster in? H2O or CH3CN
3. What kind of conditions disfavor SN1 reactions?
4. What are the products of the following reaction and does it proceed via SN1 or SN2?
5. How could you change the reactants in the problem 4 to favor the other substitution reaction?
6. Indicate the expected product and list why it occurs through SN1 instead of SN2?
2. An SN1 reaction would occur faster in H2O because it's polar protic and would stailize the carbocation and CH3CN is polar aprotic.
3. Polar aprotic solvents, a weak leaving group and primary substrates disfavor SN1 reactions.
Reaction proceeds via SN1 because a tertiary carbocation was formed, the solvent is polar protic and Br- is a good leaving group.
5. You could change the solvent to something polar aprotic like CH3CN or DMSO and you could use a better base for a nucleophile such as NH2- or OH-.
This reaction occurs via SN1 because Cl- is a good leaving group and the solvent is polar protic. This is an example of a solvolysis reaction because the nucleophile is also the solvent.
- Ashiv Sharma