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Hammond's Postulate

Hammond's postulate states that the transition state in an exothermic reaction resembles the starting materials more than the products, while in an endothermic reaction the transition state resembles the products more. This implies that the bromination of alkanes, being endothermic, has a transition state resembling an alkyl radical and HBr, leading to greater regioselectivity based on radical stability. In contrast, the exothermic chlorination has a transition state resembling the original alkane and chlorine atom, resulting in little regioselectivity.

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342 views8 pages

Hammond's Postulate

Hammond's postulate states that the transition state in an exothermic reaction resembles the starting materials more than the products, while in an endothermic reaction the transition state resembles the products more. This implies that the bromination of alkanes, being endothermic, has a transition state resembling an alkyl radical and HBr, leading to greater regioselectivity based on radical stability. In contrast, the exothermic chlorination has a transition state resembling the original alkane and chlorine atom, resulting in little regioselectivity.

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Hammond’s Postulate

“If two states, for example, a transition state


and an unstable intermediate, occur
consecutively during a reaction process and
have nearly the same energy content, their
interconversion will involve only a small
reorganization of the molecular structures”

George S. Hammond, J. Am. Chem. Soc. 1955, 77, 334-338.


Hammond’s Postulate
“The structure of the transition state for an
exothermic reaction is reached early in the
reaction, so it resembles reactants more than
products. Conversely, the structure of the
transition state for an endothermic reaction
step is reached relatively late, so it resembles
products more then reactants.”
– From your Textbook
Hammond’s Postulate
• In reactions where the
starting material is higher
in energy (A), the
transition state more
closely resembles the
starting material
• In reactions where the
product is higher in
energy (B), the transition
state more closely
resembles the product

George S. Hammond, J. Am. Chem. Soc. 1955, 77, 334-338.


Implications of Hammond’s Postulate
• In the halogenation of an alkane, hydrogen abstraction (the
rate-determining step) is exothermic for chlorination but
endothermic for bromination

H 
Reaction step [kJ (kcal)/mol]
H
+ • Cl • + H-Cl -9 (-2)
+422 (101) -431 (-103) 17 (4)
H + • Cl • + H-Cl -26 (-6)
+405 (97)
-431 (-103)
H
+ • Br • + H-Br +54 (+13)
+422 (101) -368 (-88) 17 (4)

H + • Br • + H-Br +37 (+9)


+405 (97) -368 (-88)
Implications of Hammond’s Postulate
• Because hydrogen abstraction for chlorination is exothermic,
– the transition state resembles the alkane and a chlorine atom.
– there is little radical character on carbon in the transition state.
– regioselectivity is only slightly influenced by radical stability.

H 
Reaction step [kJ (kcal)/mol]
H
+ • Cl • + H-Cl -9 (-2)
Higher in +422 (101) -431 (-103) 17 (4)
Energy
H + • Cl • + H-Cl -26 (-6)
+405 (97)
-431 (-103)
H
+ • Br • + H-Br +54 (+13)
+422 (101) -368 (-88) 17 (4)

H + • Br • + H-Br +37 (+9)


+405 (97) -368 (-88)
Implications of Hammond’s Postulate
 Because hydrogen abstraction for bromination is endothermic,
• the transition state resembles an alkyl radical and HBr
• there is significant radical character on carbon in the transition state.
• regioselectivity is greatly influenced by radical stability.
• radical stability is 3° > 2° > 1° > methyl, and regioselectivity is in the same
order.
H 
Reaction step [kJ (kcal)/mol]
H
+ • Cl • + H-Cl -9 (-2)
+422 (101) -431 (-103) 17 (4)
H • Cl • -26 (-6)
+
Higher+inH-Cl
+405 (97) Energy -431 (-103)
H
+ • Br • + H-Br +54 (+13)
+422 (101) -368 (-88) 17 (4)

H + • Br • + H-Br +37 (+9)


+405 (97) -368 (-88)
Selectivity of Halogenation Reactions

• Very small energy difference


in transition state between
primary and tertiary
chlorination transition
states. Non-Selective

• Larger energy difference in


transition state between
primary and tertiary
bromination transition
states. Selective
Hammond’s Postulate Summary
• Transition state resembles higher energy
component of reaction
• Bromination of alkanes is selective, while
chlorination is not

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