ORGANIC CHEMISTRY CHAPTER 4 structureofmolecules

Howweknowthatelectronshavedifferentenergies
Aim
Howelectrons fit intoatomic orbitals
Howatomicorbitalscombine tomakemolecularorbitals
tetrahedralstructures
Whyorganicmoleculesadoptlinearplanarand
Connection betweenshapeandelectronicstructure

Picturingtheshapeandenergyofmolecularorbitals insimplemolecules
of
Predictingthelocations lonepairsandemptyorbitals

Electronsoccupy atomicorbitals

canneverknowexactlyboth
Heisenberg's uncertainty principle we thelocationandthemomentumofanyparticle

Thehydrogenatom ThehydrideCHIion The heliumatom

also3Dandareknowasorbitalsoratomorbitals
Thevibrationanalogy vibration canadoptare
functionsknownas wavefunctions
Theshapeoftheseorbitalsare determined
bymathematical

Thenextorbitalhasonenode
zsorbital 2 becauseit'sanorbitalwithanode
s becausetheorbitalisstillspherical

Sandp orbitalshavedifferent shapes

turnsout thatforanorbitalwithonenodesuchasthevsorbitalthenodedoes notneedtobespherical
node
The can alternativelybeaplane
This
a lternative arrangementforanorbitalwithasingleplanarnodegivesusanewtypeoforbitalthezporbital

axis
unlikeis or2sorbitalstheZporbitalisdirectional itpointsalongthe Inthreedimensionstherearethreepossibleorientations
theaxiseach whichgiveriseto anewzp
for of orbital 2Paspy 2Pa
electronsarenegativelychargedandrepeloneanother
at of
thereis achoice equalenergyorbitalsthey untilthey
occupydifferentorbitalssingly
are to
f orced start
p up
airing

theboronatom thecarbonatom thenitrogenatomtheoxygenatom thefluorineatom Theneonatom

Theentiresetoforbitalsisgoingdowninenergybecausethenucleus isattractingtheelectronsmorestrongly
Thephaseofanorbital

Thereis a changeofphase ateachnode

Anodesplanecaporbitalforexample dividestheorbitalintotwopartswithdifferentphasesonewherethephase
functionispositive
andonewhereitisnegative
ofthewave
Thephasesareusuallyrepresentedbyshading

Furtherorbitalnames spdf
Fourshortclarificationsaboutorbitalsbeforewegoon
orbitalsdonotneedelectronsinthem
Electrons befoundanywhere in a orbitalexceptin anode
may say
A theseorbitalsofanatomaresuperimposed oneachotherTheisorbitalisnotthemiddlepartofasorbitalTheisandas
ownrightsbuttheasorbitaldoesoccupysomeof
orbitalsareseparateorbitalsintheir thesamespaceasthe isorbital

Aswemoveacrosssubsequentrowsoftheperoidictablestartingfromsodium theis as2porbitalsarealreadyfilledwithelectrons

sowemuststartputtingelectronsintothe35and3Porbitalsthenthe4S3DandAPorbitals
 ORGANIC CHEMISTRY CHAPTER 4 structureofmolecules

Molecularorbitals diatomicmolecules

wethinkofmolecularorbitalsasbeingbuildupfromacombinationofatomicorbitals
Thecombinationofwavescasatomicorbitalsarewavefunctions1 couldbeeitherconstructivelyCinphase ordestructively1outof
phaserTheatomicorbitalsarecombinedinthesameway

Theresultingorbitalsbelongtobothatoms theyaremolecularratherthanatomicorbitals
Forexamplethecombinationofatomicisorbitalsi
ahigherin
energy

put2e
Inuclei
inenergy
glower the
than
constituent
is
orbitals

MolecularorbitaltheoryCMOtheory ForthecaseofH
TwoatomicorbitalsCAoscombinetogivetwomolecularorbitalsCmos you thesamenumberofMosoutasyou
alwaysget
putAosin
Addingthewavefunctions combininginphase
ofthetwoAosmakesthebindingorbitalsubstitutingthemcombiningthem
outofphasemakestheantibondingorbital
thetwoatomsarethesameibothH eachAocontributesthesameamounttoMosnotalwaysthecase
Since
ThebindingMoislowerinenergythantheAOs
Theanti bindingMoishigherinenergy thantheAos
EachHatomhadinitiallyone thespinoftheseelectronsis unimportant
electron
ThezeendupintheMolowestinenergy thebindingMo
Anyorbitalmaycontainnomore than2electrons
Theze betweentwonucleiinthebondingmoholdthemoleculetogethertheyarethechemicalbond
Thesearearelowerinenergyinthemo moleculeismorestable thanitsconstituentatoms energyisgivenoutwhentheatoms
the
combine

wemustputinenergytoseparatethetwoatomsagainandtobreakthebond
Breakingbonds
promotinganelectronfromthebondingmototheantibondingMobreaksthechemicalbond
whyhydrogen is diatomicbutheliumisnot

camelout

heliumatomicorbital

Bondorder
onlyifthere'remore e inbondingMosthanantibondingMoswilltherebeanybondingbetween2atoms

FbndantibTf
fbondorde.ve tnofe inndingM0s

9 bondordert.HN i singlebond
bondorderHeu o nobond

Formingbondsusingzsandzpatomicorbitals Gand Norbitals

combining 25orbitalsaresameas is orbitals buthigherenergies Becausethe25orbitalsarehigherin

energy it'salsobiggerthan isorbitals

Thebondingorbitalsfrom is is and2525haveimportantfeatureincommon cylindricallysymmetrical

Bondingorbitalswithcylindricalsymmetrylike
thisareknownas Gsigmaorbitals
ThebondswhichresultfromputtingZeintotheseorbitalsareknowas 6bonds
TheantibondingorbitalswhichresultfromcombiningtheseHosarealsocylindricallysymmetricalandarecalled
6orbitalswith donatingtheirantibondingcharacter
Foruporbitals
Endon overlap
combinethetwo217orbitalsout phase aswiththe25 orbitals wehave a nodebetweenatoms
of
an antibondingorbital

If wecombinein phase wegetbondingorbital

6bondcanbemadefrom s or patomicorbitals providedtheyforma cylindrically symmetrical

molecularorbital

side onoverlapEachatompresentsitsother2porbitalsforside on overlap

Foroutofphasecombination

Forinphasecombination

TheseMDsdonothavecylindricalsymmetry needtorotate180abouttheaxisbetweenthenuclei
startbutwithoppositephase
beforegettingbacksthlookinglikethe
Asaresult thissymmetrywasnamedas a thebondingorbitalis aorbitalandtheantibondingorbitalis at
orbital Bondsformedbyfillingaorbitalsarecalled 2bonds
Moreoverlapispossiblewhen heAosoverlapendonthanwhen theyoverlapsideon Asaresulttheupup
orbitalislowerinenergythantheupupaorbitals
 For Nv Eachnitrogen atomcontributes7 e tothemolecule sowehavetofillthisstackof
orbitalswith14er

nitrogen atom
energyleveldiagram

Theelectrons inthe 6 bond lie between 2 nucleiwhilethe electronsinthe 2 Nbonds lie

Ekins ARITAAFG
intwoperpendicular cloudsflankingthecentral6bond

Bondorder 10 4
CNN
2 3
wecan'tignorethe e that are notinvolved inbonding 8ofthemtogetherTheycanbethought
asbeinglocalized oneachofthe Natoms

Thefour e on is orbitalsarelowenergyinnershelle that are

notinvolved inthechemistry of Nz
providethenonbonded lonepairslocatedone on

µ.foueach N atom
ORGANIC CHEMISTRY CHAPTER 4 structureofmolecules

Bondsbetween differentatoms
whathasbeenchanged
atomisdifferent
Thenumberofelectronscontributedbyeach
TherelativeenergiesoftheAosbeingcombined thegreaterthenumberofprotonsinthenucleus thegreater
theattractionandhencethemoretightlyholdmorestableandlowerinenergytheelectronbecomes

1 uronegativityThemoreelectronegativityanatomis themore itattractselectronsthelowerinenergyareitsAOs

e
increases This is
Itincreasesacrosseachrowanddecreasesdownearncolumneventhoughthenuclearcharge
becauseonceelectronsstart fillinganewsheertheyareshieldedfromthenucleusbyallthee inthelowerenergy
fieldshells contributiontonitrogenAos
havegreater
bondingorbitals

anyti
overrane distributionisskewed polarized
towards 0

Qaiaiten Ination

tooxygenAos

gofnitricoxideNo
Molecularorbitaldiagram

BondorderNo 242

wecan'teasilyrepresenthalfabondinvalencebondtermssoweusuallydraw
radical NOwithdoublebondrepresenting4bonding e
Theremaining 7 e canbeshown as 3lonepairsandoneunpairede
unpairede occupiedanorbitalclosertoN soputit onN

Fortwoatomsforming a bonddifferhugelyinelectronegativity
AOsforsodium

IIItats MeTAHITI
up 3s Nata
Endupwith
AOs forchloride

FETE HIP IEIFHEET

TheseHosaretoo
farapartinenergytocombine
toformnewMosandno covalentbond isformed
1
Molecularorbital forNau
diagram

TheionicbondinginNauisduesimplytotheattractionbetweentwooppositechargedions there'snooverlap
Summary

otherfactorsaffectingdegreeoforbitalinteraction
Aos
similarenergiesforgoodinteractionbetweentwo
Howtheorbitalsoverlap
thanitdoeswith3Pand orbitals
sizeoftheAoscaporbitaloverlapsmuchbetterwithanother zporbital

Thesymmetryoftheorbitals

ofmoleculeswithmorethantwoatoms
Molecularorbitals

pµ Amoleculeofmethane
enclosedin a cube f2sAocan
Thecarbon overlap
Thehydrogen isorbitalscanoverlap
withthethreesporbitals
withallfourhydrogenisAos
atonce

4bonds C cangiveus 25 and 3 217 while 4xHgive us 44Is

ORGANIC CHEMISTRY CHAPTER 4 structureofmolecules
Hybrization
ofatomicorbitals
Methane

Forgetting apictureofmethanewithA with4equivalent

i equivalentpairsofelectrons weneedtostart
Aos on c which we have
don't

Butwecangetifwecombinethecarbonasandzpfirsttomakefourneworbitals

0
Eachsp 3orbitaltakesthreequartersofitscharacterfroma porbitalandonequarterfroman sorbital
Ithasa planarnodethroughthenucleuslikea porbitalbutonelobeislargerthantheotherbecause theextra
of
contribution
ofthe zsorbital

Theelectronsarespatiallydistributedexactlyastheywereinourpreviousmodelbutnowwecanthink themasbeing
locatedin 4bonds
of
Ethane
3Aos orientatedtowardsthethreehydrogenatoms leavingonesp3
Eachcarbonuses3 sp orbitaloneachcarbonforthe
c cbond

Ethene ethylene
Aplanarmoleculewithbondanglescloseto1200
Inthiscaseweneed3equivalentbondsfromeachcarbonatom1onetomake a c cbondandtwotomake c Hbonds

O_O
tomakeallAosintheplane

2pm 2Pa

Thefactthatthesidewaysoverlapoftheporbitalstoform a abondisnoteffectiveastheheadonoverlapofthe
orbitalstoforma 6bondmeans ittakeslessenergytobreak a c c abondthana c c obond about200KSmoi i
comparedto350 KJmoi 1

Ethyne
Has a c cbond Eachcarbon bondstoonlytwootheratomstoform a linearskeleton
onlythecarbon and2pmhavetherightsymmetrytobondtothetwoatoms atonce leavingspyand2pztoform
aMoswiththezporbitals ontheothercarbonatom
wecanhybridizeanyatoms

Thecarbonylgroup

oxygenismoreelectronegativethancarbonhas no consequencesforthisdiagram
Firstly itmakestheenergyoftheorbitalsofa G obondlowerthan abond
thereactivityofalkenesandcarbonylcompounds
secondly polarization It receivesgreatercontributionfromtheporbitalon0thanfromtheporbitalonc

7 orbitaliscloserinenergytothe p
of
orbital ethano
a beingempty noeffectonthestructure

Irbital
ofo_0bondbutwitheffectonreactivity
iseasiertoputelectronsintotheat
orbitalat hecendthanat 0end
a ismoresimilarinenergyto
theporbitalon0than porbitalonc