Deciding SN1/SN2/E1/E2 (3) – The Solvent
Last updated: November 29th, 2022 |
There are four key factors to consider:
What’s The Solvent?
Recall that there are two important types of solvents to consider: polar protic solvents and polar aprotic solvents. [See this post: All About Solvents]
Let’s do a little review, looking at polar protic solvents first.
Polar protic solvents are solvents that are capable of hydrogen bonding. Recall that hydrogen bonding occurs where we have a highly electronegative atom such as O or N directly bonded to hydrogen. (See: The Four Intermolecular Forces And How They Affect Boiling Points)
Examples are water (H2O), alcohols (such as CH3OH , CH3CH2OH, t-BuOH) carboxylic acids (such as acetic acid) and even ammonia (NH3).
Quick N’ Dirty Tip: Solvents with OH or NH groups are polar protic solvents
Hydrogen bonding is directly responsible for the high boiling points of solvents such as water and ethanol; the partial positive charges on hydrogen are attracted to the partial negative charges on the electronegative atoms.
This is also why water is such an excellent solvent for charged species such as halide ions; hydrogen bonding solvents surround negatively charged ions like a jacket.
Polar Protic Solvents “Cling” To Nucleophiles via Hydrogen Bonding, And Nucleophilicity Goes Up As We Go Down The Periodic Table
Hydrogen bonds to nucleophiles make the nucleophile less nucleophilic!
- This “jacket” of solvent molecules – much like a protective crowd of security personnel – means that these anionic nucleophiles do not have the freedom of action they would normally have in the absence of clingy hordes of solvent molecules.
- The ability to form hydrogen bonds is highest for small, highly electronegative ions such as fluorine and decreases as ions get larger (and the charge is more diffuse) down a column of the periodic table.
- This means that in polar protic solvents, the nucleophilicity of halide anions increases as we go down the periodic table.
- So the order of nucleophilicity for halides in polar protic solvents is I(-) > Br (-) > Cl (-) > F (-) . Similarly it should be HSe(-) > HS(-) > HO (-) in the oxygen column (chalcogens)
Polar Aprotic Solvents Do Not Hydrogen-Bond With Nucleophiles, And Therefore Nucleophilicity In These Solvents Correlates With Basicity
Now let’s talk about polar aprotic solvents; polar aprotic solvents are polar enough to dissolve charged species (such as halide ions) but do not donate hydrogen bonds.
This means that in solvents such as DMSO, DMF, acetone, or acetonitrile, nucleophilicity correlates much better with basicity (and bond strength, as C-F > C-Cl > C-Br > C-I ) – and therefore nucleophilicity decreases as we go down the periodic table.
The bottom line is this:
Quick N’ Dirty Rule #5:
- Polar protic solvents tend to favor elimination (E2) over substitution (SN2)
- Polar aprotic solvents tend to favor substitution (SN2) relative to elimination (E2)
Struggling with SN1/SN2/E1/E2? Our Org 1 Summary Sheets (PDF) contain a full-page flowchart on deciding SN1/SN2/E1/E2, as well as two more pages summarizing substitution and elimination reactions, in addition to many other Org 1 topics.