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Q.What are reaction intermediates? Discuss the structure and relative stabilities of carbocation, carbanion and free radicals.

Jammu Kashmir JkboseJammu and Kashmir Board of School Education (Class 11) 2018Subjective· 5mImportance★★★★★
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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Stability: increases when the negative charge is withdrawn/dispersed, i.e. favoured by electron-withdrawing (-I) groups; alkyl groups (+I, electron-releasing) intensify the negative charge and destabilise it.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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