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SN1 and SN2: what actually decides which one happens

Both replace a leaving group with a nucleophile, and they differ in whether the bond breaks before the new one forms. SN2 does it in one motion and turns the carbon inside out; SN1 lets the leaving group go first, makes a carbocation, and whatever attacks it can attack from either face.

tert-Butyl bromide and water. The carbon is tertiary and the nucleophile is weak, so this one goes through the carbocation.

The one-step version

In SN2 the nucleophile arrives on the side opposite the leaving group and pushes it out in the same motion. There is no intermediate — bond-making and bond-breaking happen together, through a single transition state where the carbon is briefly bonded to five things.

Because the nucleophile has to reach the back face, anything crowding that carbon slows it down badly. A methyl or primary carbon is easy, secondary is sluggish, tertiary is effectively closed. And because the attack comes from behind, the carbon ends up inverted, like an umbrella in the wind. If the carbon was a stereocentre, the product has the opposite configuration.

The two-step version

In SN1 the leaving group leaves on its own, which is the slow step, and leaves behind a carbocation. The nucleophile then attacks that flat, positively charged carbon.

That ordering flips every preference. Now the question is not whether the nucleophile can reach the back of the carbon but whether the carbocation is stable enough to form at all — so tertiary is easiest and primary is effectively closed, exactly the reverse of SN2. And because the carbocation is flat, attack happens from both faces, so a single enantiomer going in gives a mixture coming out.

Reading a substrate

The substrate usually settles it. Primary carbon with a decent nucleophile: SN2. Tertiary carbon in a polar solvent that can stabilise ions: SN1. Secondary is the genuinely ambiguous case, and there the conditions decide — a strong nucleophile pushes toward SN2, a weak one in an ionising solvent pushes toward SN1.

A strong base rather than a good nucleophile changes the question entirely, because elimination starts competing for the same substrate. That is a different fork, and it is worth knowing you are at it.

Where this stops being simple

  • SN1 and SN2 are the two ends of a range, not a pair of boxes. Plenty of real reactions, particularly at secondary carbons, sit somewhere between and have kinetics that match neither cleanly.
  • The platform can draw either pathway on your own structures, but drawing a mechanism is not evidence that it is the one that runs. It is a rule-derived pathway that arrives at the product, and where two pathways both arrive, both can be drawn.

Everything here is open without an account. If you want to try the idea rather than read it, the mechanisms run on structures you supply and prediction will tell you what it thinks a flask would give, with the evidence it is reasoning from attached.