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Structure and Stability of Free Radicals

Free radicals can exist in either a planar or pyramidal configuration, with the configuration depending on the radical's hybridization state and substituents. Simple alkyl radicals prefer a planar configuration, while fluorinated derivatives like CF3 favor a pyramidal shape. Free radicals are formed through homolytic bond cleavage via thermal, photochemical, chemical, or redox reactions. The stability of free radicals can be explained by hyperconjugation, with N,N-diphenyl picryl hydrazyl being the most stable due to resonance stabilization.

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431 views8 pages

Structure and Stability of Free Radicals

Free radicals can exist in either a planar or pyramidal configuration, with the configuration depending on the radical's hybridization state and substituents. Simple alkyl radicals prefer a planar configuration, while fluorinated derivatives like CF3 favor a pyramidal shape. Free radicals are formed through homolytic bond cleavage via thermal, photochemical, chemical, or redox reactions. The stability of free radicals can be explained by hyperconjugation, with N,N-diphenyl picryl hydrazyl being the most stable due to resonance stabilization.

Uploaded by

anil
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Free Radical

Structure of Free Radicals


• Similar to carbanions, carbon containing an unpaired electron(s) in free radicals also
may either be in sp2 hybrid state in which case the structure would be planar with odd
electron in the p orbital or it could be sp3 hybridised which would make the structure
pyramidal (non-planar) and the odd electron will be in one of the sp3 orbitals.
• Planar
• Pyramidal
• Physical and chemical evidences (E.S.R and stereochemistry) point to a planar
configuration at o the radical centre for simple alkyl radicals but not for fluorinated
derivatives (e.g., CF3) which prefer pyramidal shape.
• In resonance stabilised free radicals the radical carbon is certainly in sp2 hybrid
state.
Structure of Free Radical
Formation of Free Radical
• Free radicals are formed by homolytic fission of a
covalent bond, when a molecule is supplied with sufficient
energy--thermal or photochemical.
• (i) Thermal cleavage: Most of the covalent bonds are
thermally stable upto a temperature of 200°C, used in
solution chemistry. However, there are a few group of
compunds (peroxy and azo) which undergo homolytic
cleavage at temperatures below 200°C.
Free Radicals formation from peroxides
• (ii) Photochemical cleavage: radical is generated through irradiation with either UV or
visible light.
• The energy transferred to the molecule by the interaction must be of the order of bond
dissociation energy or greater to produce homolysis.
• (iii) Chemical method

• (iv) Redox reactions


Stability of free Radical
• The stability order of free radicals can
be explained by hyperconjugation.
MostStable Free Radical
• The most stable free radical is N, N-diphenyl picryl hydrazyl. This free radical is a
commercially available soild.

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