Q.What are reaction intermediates? Discuss the structure and relative stabilities of carbocation, carbanion and free radicals.
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Start your 14-day free trial to unlock the full solution →Reaction intermediates (carbocations, carbanions, free radicals) are short-lived species formed mid-mechanism; their stability order depends on how well the substituents can supply or withdraw electron density and delocalise the charge/unpaired electron.
What are reaction intermediates?
Many organic reactions do not occur in a single step; instead, the reactant is converted to the product via one or more unstable, high-energy, short-lived species called reaction intermediates, which exist only momentarily before reacting further. The three most important carbon-centred intermediates are carbocations, carbanions and free radicals.
Carbocation
A carbocation is formed when a bond breaks heterolytically and the carbon atom keeps only 6 electrons in its valence shell, carrying a positive charge, e.g. R3C+. The positively-charged carbon is sp2 hybridised, planar, with an empty p orbital.
Stability: increases with the number of alkyl groups attached, because alkyl groups release electron density towards the positive carbon by the +I (inductive) effect and by hyperconjugation, spreading out (delocalising) the positive charge.
Order: 3 degree (tertiary) > 2 degree (secondary) > 1 degree (primary) > methyl carbocation.
Carbanion
A carbanion is formed when a bond breaks heterolytically and carbon retains both bonding electrons plus its lone pair, carrying a negative charge, e.g. R3C:-. It is sp3 hybridised and pyramidal (like NH3).
Stability: increases when the negative charge is withdrawn/dispersed, i.e. favoured by electron-withdrawing (-I) groups; alkyl groups (+I, electron-releasing) intensify the negative charge and destabilise it.
Order: methyl carbanion > 1 degree > 2 degree > 3 degree (exactly opposite to the carbocation order).
Free radical
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