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SN1 versus SN2 reactions: A Complete Chart Summary

Before we start our discussion of the SN1 and SN2 reactions, let's get introduced to some of the terms.

Both reactions are nucleophilic substitution reactions. What that means is that a nucleophile will replace (substitute) something in the starting material. What does it replace? A leaving group. The molecule with the leaving group is called a substrate (starting material).

SN1 versus SN2 Summary Chart
SN1 versus SN2 Summary Chart


The chart above summarizes both reactions and major differences between them. Let's take a more in depth look at each one.

SN2

Steps and Mechanism: SN2 is a 1 step reaction. The leaving group leaves and, at the same time, nucleophile attacks the carbon with the leaving group from the back.


Stereochemistry: The reaction results in an inversion. If the leaving group was on a wedge, nucleophile will be on a dash. If the leaving group was on a dash, nucleophile will be on a wedge. If the leaving group was up, nucleophile will be done and vice versa.


Kinetics: The rate of the reaction depends on both the substrate and nucleophile. This reaction is said to be bimolecular.


Substrate: SN2 prefers primary substrate (leaving group is attached to a carbon that is attached to one carbon only). It is ok with secondary substrate but never tertiary. This is because nucleophile attacks from the back and if there are too many groups in the back, nucleophile will simply not be able to get through to the carbon.


Nucleophile: SN2 prefers strong nucleophile. Strong nucleophiles usually have a negative charge and this makes it easer to spot them. Oftentimes, negatively charged anions are together with spectator ions such as Na+, Li+ and K+. For example, NaOH might look neutral. However, Na+ is the spectator ion. OH- is the nucleophile (and it is negatively charged).

Examples of strong nucleophiles are: OH-, RO-, RS-, I-, CN-, I-, Br-


Solvent: SN2 prefers polar aprotic solvent (no hydrogen connected to an electronegative atom). This solvent increases the energy of the nucleophile.

Examples of polar aprotic solvents: DMSO, DMF, CH3CN


SN1

Steps and Mechanism: SN1 is a two step reaction (sometimes more than two steps are needed). In step 1, leaving group leaves forming a carbocation. In step 2 nucleophile attaches to the carbocation. If the nucleophile is H2O or ROH, a third step is needed to deprotonate (take off an H) from the group that attached.


Stereochemistry: The reaction gives two products. One with the same stereochemistry (retention). For example if the leaving group was on a wedge, nucleophile would be on a wedge in the product as well. Another product is with an inversion of stereochemistry. For example, if the leaving group was on a wedge, nucleophile in the product would be on a dash. The two products together are called a racemic mixture.


Kinetics: The rate of SN1 reaction depends on the step of the leaving group leaving (rate determining step) and therefore depends on the substrate only (unimolecular).


Substrate: SN1 prefers tertiary substrate, ok with secondary, never primary (unless resonance stabilized, please consult with your professor in regards to this point as it differs from one college to another).

The reason SN1 prefers tertiary substrate is because the more substituted a carbocation is, the more stable it is. The more stable carbocation is, the more likely the reaction is to proceed since creating carbocation is the rate determining step. Therefore, carbocations that are stabilized via resonance are also favored by SN1.


Nucleophile: SN1 prefers weak nucleophile. Generally, weak nucleophile are neutral (not always). Examples of weak nucleophiles are : H2O, ROH, F-


Solvent: SN1 prefers polar protic solvent ( contains a hydrogen attached to an electronegative atom). Polar protic solvents stabilize the carbocation.

Examples of polar protic solvents are: H2O, ROH, NH3, RCOOH.


Leaving Group:

Both reactions SN1 and SN2 want as good of a leaving group as possible. A good leaving group, when it leaves, is stable on its own, and does not want to attack the molecule back.

Examples of good leaving groups: I->Br->Cl-> OTS-> H2O






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