Chemistry Tutorial: Aromaticity

Based on a Chemistry 14C Honors Project

Sixcarbonsonceformedinaring,
withsp2hybridization.
Thestrainwasrelieved,
andallsixachieved
electrondelocalization

Thestability,itselfisdramatic,
saidapuzzledochemistfanatic.
Allthesefactorsatwork
justaddanewperk.
Andthuswasproclaimedaromatic.

Contents

Section1:Vocabulary
Section2:DeterminingAromaticity
Section3:ConjugationandAromaticity
Section4:ResonanceandAromaticity
Section5:FrequentlyAskedQuestions
Section6:CommonErrors
Section7:ReadingsandSources

Section1:Vocabulary

(a)Defineeachterm
(b)Explainhowitrelatestoaromaticity

Aromaticity

Conjugation

Cyclicdelocalization

Resonance

Pibonds

PartialPibonds

RingStrain

Section1:VocabularySolutions

Aromaticity
a) Extra stability possessed by a molecule that meets specific criteria: pi bonds all must lie
within a cyclic structure, loop of p orbitals, p orbitals must be planar and overlap, must
followHckelsRule.
b)n/a

Conjugation
a)Thespecialstabilityprovidedbythreeormoreadjacent,parallel,overlappingporbitals.
b)Aromaticmolecules,bydefault,haveconjugation.Asittakesaminimumofthree,adjacent,
overlapping p orbitals for planarity, aromaticity requires a minimum of this for
conjugation.Aromaticityislikeconjugation,butextrastable.

Cyclicdelocalization
a)Electrondelocalization,ordistributionofelectrondensity,occursasaresultofoverlapping
porbitalsinaplanar,cyclicstructure.
b)Aclosedloopofoverlappingporbitalsmustbepresentforaromaticitytooccur;therefore,
cyclicdelocalizationoccursinaromaticmoleculesandisacontributortothemolecules
extrastability.

Resonance
a)AsituationinwhichamoleculecanberepresentedbytwoormorevalidLewisstructures.
b) By looking at resonance structures such as a benzene ring, we can determine where p
orbitalsandpartialpibondsoccur.Partialpibondsandplanarporbitalscancontribute
toaromaticity,soresonancealsocontributestothestabilityofaromaticmolecules.

Pibonds
a)Pibondsareformedbytheoverlapofporbitalsbetweentwoadjacentatoms.
b)Inorderforamoleculetohavearomaticity,itmustfirsthavepibondssothatoverlapping
porbitalsandelectrondelocalizationarepresent.

PartialPibonds
a)Partialpibondsareformedasaresultofclosepibondslyinginthesameplane.
b) Through resonance, aromatic molecules achieve conjugation and a ring of overlapping p
orbitalsthroughpartialpibondswithinastructure.

RingStrain
a)Ringstrainoccursasacombinationoftorsionalandanglestrainandfromdeviationfrom
theidealorpreferredbondangles.
b)Becausearomaticmoleculesincludeaclosedringofporbitals,ringstrainoccurs;however,
thebenefitsofaromaticitygenerallyoutweightheringstrainintermsofmolecular
stability.

ChecktheIllustratedGlossaryofOrganicChemistry(availableatthecoursewebsite)for
moredefinitions.

Section2:DeterminingAromaticity

Overview:

Aromaticityisspecialstabilityprovidedtoamoleculeuponpossessingfourspecific
qualitiesmentionedbelow.Todetermineifamoleculeisaromatic,investigateitsstructure
forthequalifiers.Ifallarepresentwithinthemolecule,thenitisaromatic.

CriteriaforAromaticity:
Pibondsmustliewithincyclicstructure
Eachatominthecyclemusthaveporbital,formingporbitalloop
Allporbitalsintheloopmustoverlap(planarity)
HckelsRule:orbitalarrangementmustresultinaloweringofenergy.4n+2pi
electrons(nisaninteger:0,1,2,3,etc)intheloop

ExampleProblem:
Determineifthefollowingmoleculeisaromatic.

Step1:Dopibondsliewithinacyclicstructure?

Threepibondsarepresent,eachlyingwithin

thecyclicstructureofbenzene

Yes

Step2:Doeseachatominthecyclehaveaporbital,formingaporbitalloop?

Eachatomhasaporbital,formingaloop

Yes

Step3:Doallporbitalsoverlapandliewithinthesameplane?

Byrotatingthemolecule,weseethatall

orbitalsliewithinthesameplane

Yes

Step4:DoesthemoleculefollowHckelsRule?

6totalpielectrons
4n+2=6
n=1

Yes

Conclusion:Benzeneisanaromaticmolecule

PracticeProblems:

Determinewhetherornotthefollowingmoleculesarearomatic.

PracticeProblems:Solutions

1.Yes;meetsallcriteria

2.No;doesnotincludeloopofoverlappingporbitals

3.No;doesnotcontainloopofoverlappingporbitals

4.Yes;meetsallcriteria

5.No;doesnotfollowHckelsRule

6.Yes;meetsallcriteria

Section3:ConjugationandAromaticity

Overview:

Conjugationrequiresatleastthreeoverlappingporbitalsinthesameplanesothat
electrons can be delocalized for better stability. Aromaticity cannot exist without
conjugation because aromatic molecules require planarity and overlapping p orbitals.
However,conjugationcanexistinamoleculewithoutbeingaromatic.

ExampleProblem:

Determineifthemoleculebelowhasconjugation,aromaticity,both,orneither.

Step1:Doesthemoleculehaveconjugation?

Yes,theatomsareallplanarwithmorethan

threeoverlappingporbitals

Step2:Isthemoleculearomatic?

Pibondsarepresentwithinacyclicstructure

Eachatomhasaporbital,formingaloop

Porbitalsoverlapandlieinthesameplane

ViolatesHckelsRule(4n+2=8;n=6/4)

Notaromatic

Conclusion:Themoleculehasconjugation,butisnotaromatic.

PracticeProblems:ConjugationandAromaticity:

Determineifthemoleculesbelowhaveconjugation,aromaticity,both,orneither.

1.

4.

2.

5.

3.

6.

N
H

PracticeProblemsSolutions

1. Not conjugated (the molecule has a tub shape and the C=C are perpendicular); Not
aromaticviolatesHckelsrule

2. Not conjugated does not contain at least three atoms with planar p orbitals; Not
aromaticdoesnotcontainclosedloopofplanar,overlappingporbitals

3.Conjugated;Aromaticmeetsallcriteria

4.Conjugated,Notaromaticdoesnotcontainclosedloopofplanar,overlappingporbitals

5.Conjugated;Aromaticmeetsallcriteria

6.Conjugated;Aromaticmeetsallcriteria

Section4:ResonanceandAromaticity

Overview:

Resonance exists as a result of electron delocalization in a molecule. Different

patterns emerge as a result of structure and atom arrangement within a molecule.
Resonance provides an extra stability due to electron delocalization, and consequently;
aromatic rings have resonance structures due to cycling double bonds. Aromatic
molecules must have resonance; however, not all molecules with resonant structures are
aromatic.

ExampleProblem:

Determineifthemoleculebelowhasresonance,aromaticity,both,orneither.

Step1:Doesthemoleculehaveresonance?

Thepibondsinthemoleculecanswitchplaces,apropertyseeninalkene
rings,resultinginaresonancehybrid:

HasResonance

Step2:Isthemoleculearomatic?

Yes,theatomsareallplanarwithmorethan

threeoverlappingporbitals

Pibondsarepresentwithinacyclicstructure

Eachatomhasaporbital,formingaloop

Theporbitalsoverlapandlieinsameplane

SatisfiesHckelsRule(4n+2=14;n=3)

Aromatic

Conclusion:Themoleculehasresonance,andisaromatic.

PracticeProblems:ResonanceandAromaticity

Determineifthemoleculesbelowhaveresonance,aromaticity,both,orneither.

CH3CH2CH2NH2

PracticeProblems:Solutions

1.Noresonance;Noaromaticity.

2.Resonance;Noaromaticity

3.Resonance;Aromaticity

4.Noresonance;NoAromaticity

5.Resonance;NoAromaticity

6.Resonance;Aromaticity

Section5:FrequentlyAskedquestions

Areconjugationandaromaticitythesamething?
o Notquite.Conjugationoccursinaromaticmolecules,butaromaticityisahigher
levelofstabilitywithmorerequirementstobemet.Conjugationcanbeviewed
assimplyapieceofaromaticity.

Whywouldamoleculeprefertobearomatic?
o Equilibriumfavorsstability.Aromaticmoleculeshaveaspecialextrastability
causedbythenatureoftheirstructure,andarehardertobreakapart.

HowcanItellifamoleculewithNitrogenisaromatic?
o Itdependsonthemolecule.Ifnitrogenispartofaring,checkitshybridization
andelectrons.Ifitissp2hybridizedorifitcanbecomesp2hybridizedasaresult
oftheoverallstructureandelectrondelocalizationofthemolecule,themolecule
isaromatic.

Whatdolonepairshavetodowitharomaticity?
o Lonepairscanleadtoresonancehybridsorresideinpibondsthatcontributeto
thearomaticityofamolecule.

Canpurelylinearmoleculeshavearomaticity?
o No. A requirement for aromaticity is a closed loop or ring orp orbitals. Since
linearmoleculescannotachievethis,theyareunabletobeclassifiedasaromatic.

Ifamoleculecontainsanaromaticring,suchasabenzenering,attachedtoanon
aromaticring,howdoesthataffecttheoverallaromaticityofthemolecule?
o Overall,amoleculecanfailtomeetthequalificationsforaromaticityasawhole,
but still contain aromatic parts. If a molecule contains a benzene ring, we can
saythatthemoleculehasanaromaticring,butwecannotsaythatthemolecule
isaromatic.


o Example:Withintheabovemolecules,therearearomaticparts,outlinedinred.
However,themoleculesasawholearenotaromatic.

What does the n of Hckels Rule represent, and what does it mean if it is an
integerornotaninteger?
o ThenofHckelsRuleissimplyanindicatorofaromaticity.Itdoesnotstand
foracertainword,butisinsteadusedasacalculator.Ifnisawholenumber
integer,themoleculecanbearomatic,andifnisafractionornoninteger,the
moleculeisnotaromatic.

HowcanItellifamoleculehasplanarity?
o The best way is to build a model. Remember that to have a planar loop of p
orbitals, the molecule must have at least three points of interest, atoms or p
orbitals,inordertoformaplane.Afteryouhavedeterminedthis,checktoseeif
theatomshaveporbitals,andthattheyareadjacent.

Doesanaromaticmoleculeneedtohaveconjugationandresonance?
o Aromaticmoleculesmusthaveconjugation,andgenerally,becausetheycontain
a series of p orbitals and pi bonds, resonance occurs. An aromatic molecule
always has conjugation and resonance, but not all molecules that have
conjugationand/orresonancearealsoaromatic.

HowdoIcountthepielectronstoplugintotheequationofHckelsRule?
o HckelsRule(4n+2=#pielectrons)appliesonlytothepielectronspresentin
the closed loop of p orbitals. Find the p orbitals present in molecule and
determinethenumberofelectronsineach.Sometimes,thisisveryapparent,as
doublebondsimplytwopielectrons.Becareful,though,asoxygenandnitrogen
atomscansometimeshaveanemptyporbital,orelectronscanbeforcedintoa
porbitaltoachieveconjugationandaromaticity.

Section6:CommonErrors

AromaticityofFuranandPyrrole

N
H

Furan
Pyrrole

Furanandpyrrolearebotharomaticmolecules.Atfirstsight,thesemoleculesseem
to be nonplanar without a closed loop of p orbitals; however, because of the benefits of
achieving aromaticity, the structure is such that two lone pair electrons are delocalized,
shownbelow:

By looking at the resonance hybrid, we can see the

delocalizationofonelonepairofelectronsontheoxygen.

Theotherelectronpairislocatedsomewhereintheporbitalof
oxygen,whichisnowsp2hybridized.

The electrons are delocalized

throughout the planar ring,
creatingacloudofpielectrons.

In a final determinant of aromaticity, by counting the pi

electrons,weseethatfuranfollowsHckelsrule.

CountingPielectrons

Whatisapielectron?

o Apielectronisanelectroninvolvedinapibond.

Whatisapibond?

o Apibondisanoverlapoftwoadjacentporbitalsbetweentwoatoms.

DoubleBonds:

o Consistof1sigmabondand1pibond.

o Apibondcontains2pielectrons.

o Therefore,whencountingpielectrons,youknowthatforeachdoublebond,
therearetwopielectronspresent.

BeCareful:Furan/Pyrrole:

o Sometimes, resonance will cause sp3 atoms to become sp2 hybridized.

Electrondelocalizationandaromaticityisachievedbydelocalizingonelone
pair, which will count as two pi electrons in the system for the purpose of
Hckelsequation.

Section7:OtherReadingsandExtraSourcestoConsult

AromaticityinChemistry14CBooks:

Chemistry14CThinkbook

Chemistry14CLectureSupplement

OrganicChemistryasaSecondLanguage(Klein)

OrganicChemistry:StructureandFunction(VollhardtandSchore)andStudyGuide

OnlineWebsites

"Aromatic Compounds and Aromaticity." Dr Andy Cammidge's Homepage. University of

EastAnglia.24Nov.2008<http://www.uea.ac.uk/~c286/aromaticnotes.htm>.
This website gives great insights about the basics of aromaticity, general
concepts, and related vocabulary. It also gives indepth views of aromatic
compoundsandthequantummechanicsbehindtheirelectrondelocalization.

"AromaticityandHckel'sRule."O=CHem.UniversityofSouthernMaine.24Nov.2008
<http://web1.uct.usm.maine.edu/~newton/Chy251_253/Lectures/Aromaticity/AromaticityFS.html>

This website talks about Hckels rule. It specifically elaborates about the
electron placement in aromatic rings and compounds, relating it back to
molecularorbitals,bonding,andhowhybridizationworks.

Wikipedia."Aromaticity."Aromaticity.14Nov.2008.Wikipedia:TheFreeEncyclopedia.24
Nov.2008<http://en.wikipedia.org/wiki/aromaticity>.
Although this site does not go in depth like the others, it provides useful
information about the general topic of aromaticity, the qualifications, and
molecularstructure.

Wikipedia."Furan."Furan.14Nov.2008.Wikipedia:TheFreeEncyclopedia.24Nov.2008
<http://en.wikipedia.org/wiki/furan>.
Thispagespecificallytalksaboutwhyfuranachievesaromaticity.Itprovidesa
usefuldiagramoftheresonancestructuresandelectrondelocalizationleadingto
stability.