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SN2Reaction

TheSN2Reaction
ThismoviedepictsanSN2reactionbetweenthehydroxideanion(HO)andmethylchloride.Inthis
reaction,anewbondisformedbetweenthenucleophile,HO,andthecarbonatom,whilethe
carbonchlorinebondisbroken.Thedepartingchlorideanionisreferredtoastheleavinggroup.
Thespeciesbeingattackedbythenucleophile,namelymethylchloride,isreferredtoasthe
electrophile.
ThetermSN2standsforSubstitutionreaction,Nucleophilic,2ndorder(alsocalledbimolecular).
AccordingtotheSN2mechanism,thereisasingletransitionstatebecausebondbreakingandbond
makingoccursimultaneously.Noticethatforthistooccur,thenucleophilemustapproachfromthe
backsideofthecarbonleavinggroupbond(socalledbacksideattack).Lookforthebacksideattack
inthemovie.

NoticethatthereisnotintermediateinanSN2reaction,justatransitionstate.Atransitionstatehas
noreallifetime,itisthehighestenergypointonthereactioncoordinateasstartingmaterials
transitionintoproducts.
BimolecularreactionAbimolecularreaction,suchastheSN2reaction,isoneinwhichtwo
reactantstakepartinthetransitionstateofthesloworratedeterminingstepofareaction.Forthis
reason,theconcentrationsofboththenucleophileandthealkylhalideareproportionaltothe
observedSN2reactionrate.
NucleophilicityBecausethenucleophileisinvolvedintheratedeterminingstepofSN2reactions,
strongernucleophilesreactfaster.Strongernucleophilesaresaidtohaveincreasednucleophilicity.
Inthegasphase,thereisacorrelationbetweenincreasedrelativenucleophilicityandincreasedbase
strength,althoughtherearemanyexceptionstothistrendinsolution(seebelow).Ingeneral,within
aperiodoftheperiodictable,nucleophilicityincreasesfromrighttoleft.Furthermore,fordifferent
reagentswiththesamenucleophilicatom,ananionisabetternucleophilethananeutralspecies.
SolventeffectsInsolutionthecomparisonofnucleophilicityvs.basicityiscomplicatedbysolvation
effects.Polaraproticsolvents(e.g.acetonitrile,dimethylsulfoxide,dimethylformamide,etc.)are
goodatsolvatingcations,butnotanions.Asaresult,thenucleophilesarenothighlysolvated,and
therelativeorderofnucleophilicitiesissimilartothatobservedinthegasphase.Polarprotic
solvents(e.g.alcohols,water)aremuchbetteratsolvatinganions,sonucleophilesarehighly
solvatedinthesesolvents.Therelativeorderofnucleophilicitiescanbechangeddramaticallybythis
solvation.Solvationofnucleophilesbypolarproticsolventsalsoinhibitsthenucleophilesabilityto
takepartinanSN2reaction,soSN2reactionsaremuchslowerinpolarproticsolventscompared
withpolaraproticsolvents.
InversionofstereochemistryIfthehalideleavinggroupisattachedtoastereocenter,the
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SN2Reaction

configurationofthestereocenterisinvertedduringanSN2reaction.Thisisbecausethenucleophile
entersfromtheoppositesideofthemoleculeasthedepartinggroup(backsideattack),thusthe
moleculeinvertsanalogoustoanumbrellainvertinginthewind.Youcanseethismolecular
inversionintheabovemovie,butinthiscase,theinversiondoesnotinfluencestereochemistrysince
neitherthereactantsnorproductsarechiral.
InhibitionbysterichindranceSN2reactionsareparticularlysensitivetostericfactors,sincethey
aregreatlyretardedbysterichindrance(crowding)atthesiteofreaction.Ingeneral,theorderof
reactivityofalkylhalidesinSN2reactionsis:methyl>1>2.The3alkylhalidesaresocrowded
thattheydonotgenerallyreactbyanSN2mechanism.

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