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

Conclusion:Benzeneisanaromaticmolecule PracticeProblems: Determinewhetherornotthefollowingmoleculesarearomatic.

Step4:DoesthemoleculefollowHckelsRule? 6totalpielectrons 4n+2=6 n=1 Yes

PracticeProblems:Solutions 1.Yes;meetsallcriteria 2.No;doesnotincludeloopofoverlappingporbitals 3.No;doesnotcontainloopofoverlappingporbitals 4.Yes;meetsallcriteria 5.No;doesnotfollowHckelsRule 6.Yes;meetsallcriteria

Section3:ConjugationandAromaticity Overview: Conjugationrequiresatleastthreeoverlapping porbitalsinthesameplanesothat 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.
N H

3. 6.

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.
O

1 4

2 5

3 6
S

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 or p 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 atomscansometimeshaveanempty porbital,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>

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.

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.