MadSci Network: Chemistry
Query:

Re: Addition of bromine to ethyne

Date: Thu Aug 10 14:19:12 2000
Posted By: Jerry Franzen, Faculty Chemistry
Area of science: Chemistry
ID: 964646474.Ch
Message:

When a double or triple bond is attacked by an electrophilic (electron 
seeking) species, the carbon atoms in the multiple bond must bear some 
electron deficiency.  In the case of the addition of HX, one carbon must 
bear all of the deficiency; in the case of adding Br2, the carbons share 
the deficiency.  It is the initial attack of the Br2 that determines the 
rate (speed) of the reaction.

A major difference between the double bond and the triple bond lies in the 
hybridization of the bonding orbitals on the carbons.  In the double bond 
the hybridization is sp2, whereas it is sp for the triple bond.  The sp 
hybridized carbon atom does not handle the electron deficiency as well as 
the sp2 hybridized carbon. Stated another way, the electron deficient sp 
carbon is of higher energy than the sp2 counterpart.  The higher energy of 
the sp intermediate makes its attainment more difficult and slows the 
reaction in comparison to that for the sp2 carbon, since the attack by the 
electrophile is the "rate-determining step."

If you have studied about this reaction enough to understand 
the "bromonium ion" description, this argument fits well with that 
description also, because, even though we show all of the electron 
deficiency on the bromine with a + charge in that description, it 
certainly must pass this deficiency on to the less electronegative carbons.

Dr. Jerry Franzen
Chemistry Department
Thomas More College
859-344-3377
franzenj@thomasmore.edu


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