Part of OC-04 — Haloalkanes & Haloarenes

SN1 vs SN2 — Detailed Mechanistic Cornell Note

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QUESTIONS / CUESNOTES
Rate law difference?SN1: Rate = k[RX] — only substrate. SN2: Rate = k[RX][Nu-] — both substrate and nucleophile.
Intermediate in SN1?Carbocation (R+) — planar, sp2, trigonal planar geometry.
Intermediate in SN2?NONE — single transition state only. Pentacoordinate transition state (5 groups on C).
Can SN1 give rearrangement?YES — carbocation can undergo 1,2-hydride or 1,2-methyl shift to more stable carbocation before Nu attack.
Can SN2 give rearrangement?NO — concerted single step, no intermediate → no opportunity for rearrangement.
Effect of [Nu] on SN1?No effect — Nu not involved in rate-determining step (RDS). Doubling [Nu] → rate unchanged.
Effect of [Nu] on SN2?Proportional — Rate = k[RX][Nu]. Doubling [Nu] → rate doubles.
How to choose between SN2 and E2?Strong non-bulky Nu → SN2. Strong bulky base (t-BuO-) → E2 (can't access C-X, abstracts β-H instead).
Example: SN1 product(CH3CH_{3}){3}CBr + H2OH_{2}O → (CH3CH_{3}){3}COH + HBr. Product: tert-butanol SMILES: CC(C)(C)O.
Example: SN2 product(R)-CH_{3}$$CHBrCH_{2}$$CH_{3} + NaOH (DMSO) → (S)-CH3CH_{3}CH(OH)CH_{2}$$CH_{3}. Complete R→S inversion.
Competition at 2° substrate?2° can undergo either SN1 or SN2. Strong Nu + aprotic → SN2. Weak Nu + protic → SN1.
What is "common ion effect" in SN1?Adding excess X- (same leaving group) shifts SN1 equilibrium backward → slows product formation.
Solvent effect on nucleophile?Protic: solvates Nu- (cage effect) → weaker Nu → SN2 slower. Aprotic: Nu- is naked → stronger → SN2 faster.
Rate order for SN2 substrates?Methyl > Primary > Secondary > Tertiary (inverse of SN1 substrate order).

SUMMARY ROW: SN1 and SN2 are distinguished by: (1) rate law (mono vs bimolecular), (2) substrate type (3° vs 1°), (3) nucleophile (weak vs strong), (4) solvent (protic vs aprotic), (5) stereochemistry (racemization vs inversion), (6) rearrangement possibility (yes in SN1, no in SN2). The most NEET-tested distinction: SN2 always gives Walden inversion; SN1 always gives racemization for chiral substrates.

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