The SN2 reaction (also known as bimolecular nucleophilic substitution) is a type of nucleophilic substitution, where a lone pair from a nucleophile attacks an electron deficient electrophilic center and bonds to it, expelling another group called a leaving group. Thus the incoming group replaces the leaving group in one step. Since two reacting species are involved in the slow, rate-determining step of the reaction, this leads to the name bimolecular nucleophilic substitution, or SN2. Among inorganic chemists, the SN2 reaction is often known as the interchange mechanism.
SN2 attack occurs if the backside route of attack is not sterically hindered by substituents on the substrate. Therefore this mechanism usually occurs at an unhindered primary carbon centre. If there is steric crowding on the substrate near the leaving group, such as at a tertiary carbon centre, the substitution will involve an SN1 rather than an SN2 mechanism, (an SN1 would also be more likely in this case because a sufficiently stable carbocation intermediary could be formed.)
The Size of the Nucleophile. How readily a compound attacks an electron-deficient atom also affects an SN2 reaction. As a rule, a negatively charged species (e.g. OH -) are better nucleophiles than neutral species (e.g. H2O, water). There is a direct relationship between basicity and nucleophilicity: stronger bases are better nucleophiles. Acidity, the ability of an atom to give up a proton (H+), is comparatively relative when molecules whose attacking atoms are approximately the same in size, the weakest going toward the left side of the periodic table. If hydrogen were attached to second-row elements of the periodic table, the resulting compounds would have the following relative acidities:
If each of these acids were to give up a hydrogen, the result would be its conjugate base, and the relative strengths will reverse. The stronger base now moves toward the left side of the periodic table.
Elements increase in size down the periodic table. Although basicity decreases down the periodic table, nucleophilicity increases as size increases depending on the solvent used.
Solvent. If a reaction is carried out in a protic solvent, whose molecules have a hydrogen bonded to an oxygen or to a nitrogen, the larger atom is a better nucleophile in an SN2 reaction. In other words, the weaker base is the better nucleophile in a protic solvent. For example, the iodide ion is better than a fluoride ion as a nucleophile. However, if the reaction is carried out in an aprotic solvent, whose molecules do not have hydrogen bonded to an oxygen or to a nitrogen, then the stronger base is the better nucleophile. In this case, the fluoride ion is better than the iodide ion as a nucleophile. Sterics. Steric hindrance is any effect of a compound due to the size and/or arrangement of its substituent groups. Steric effects affect nucleophilicity but does not affect base strength. A bulky nucleophile, such as a tert-butoxide ion with its specific arrangement of methyl groups, is a poorer nucleophile than an ethoxide ion with a straighter chain of carbons, even though tert-butoxide is a stronger base.
This is a key difference between the SN1 and SN2 mechanisms. In the SN1 reaction the nucleophile attacks after the rate-limiting step is over, whereas in SN2 the nucleophile forces off the leaving group in the limiting step. In other words, the rate of SN1 reactions depend only on the concentration of the substrate while the SN2 reaction rate depends on the concentration of both the substrate and nucleophile. In cases where both mechanisms are possible (for example at a secondary carbon centre), the mechanism depends on solvent, temperature, concentration of the nucleophile or on the leaving group.
It is important to understand that SN2 and SN1 are two extremes of a sliding scale of reactions, it is possible to find many reactions which exhibit both SN2 and SN1 character in their mechanisms. For instance, it is possible to get a contact ion pairs formed from an alkyl halide in which the ions are not fully separated. When these undergo substitution the stereochemistry will be inverted (as in SN2) for many of the reacting molecules but a few may show retention of configuration.
With ethyl bromide, the reaction product is predominantly the substitution product. As steric hindrance around the electrophilic center increases, as with isobutyl bromide, substitution is disfavored and elimination is the predominant reaction. Other factors favoring elimination are the strength of the base. With the less basic benzoate substrate, isopropyl bromide reacts with 55% substitution. In general, gas phase reactions and solution phase reactions of this type follow the same trends, even though in the first, solvent effects are eliminated.