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Chapter 8: Nucleophilic Substitution



Summary | Overview | SN1 | Carbocations | SN2 | Nucleophiles | Nucleophilicity versus Basicity | Leaving Groups | Solvent Effects | Substitution versus Elimination | Substitution reactions involving Alcohols | Substitution reactions of Alkyl Halides | Self Assessment | Quiz |


Carbocations

Chapter 8: Nucleophilic Substitution

Stability:
The general stability order of simple alkyl carbocations is: (most stable) 3o > 2o > 1o > methyl (least stable)

[carbocation stability order]

This is because alkyl groups are weakly electron donating due to hyperconjugation and inductive effects. Resonance effects can further stabilize carbocations when present.

Structure:
 
A simple representation of a carbocation
Alkyl carbocations are sp2 hybridized, planar systems at the cationic C center. 
The p-orbital that is not utilized in the hybrids is empty and is often shown bearing the positive charge since it represents the orbital available to accept electrons.
Computer model of CH3+

Reactivity:

electrostatic potential of CH3+ (side view) As they have an incomplete octet, carbocations are excellent electrophiles and react readily with nucleophiles. Alternatively, loss of H+ can generate a p bond. 

The electrostatic potential diagrams clearly show the cationic center in blue, this is where the nucleophile will attack.
 

electrostatic potential of CH3+ (top view)

Rearrangements:
Carbocations are prone to rearrangement via 1,2-hyride or 1,2-alkyl shifts if it generates a more stable carbocation

Reactions involving carbocations:
1. Substitutions via the SN1
2. Eliminations via the E1
3. Additions to alkenes and alkynes (HX, H3O+)



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