Chemistry3810LectureNotesDr.R.T.

BoerPage148

6.TheHalogensandtheirCompounds
We now come to our coverage of Chapter 12, which deals with the Groups 17 and 18 elements, i.e. the
halogens and the noble gases. The redox chemistry of the oxoacids and anions was discussed extensively in
Chemistry 2810 I suggest you look back atyournotesandtoChapter6(theredoxchapter)torefreshthismaterial
inyourmind.

6.1Theelements
These are all diatomic molecular compounds. We have already discussed the MO structures of the first row
diatomicmolecules.RememberfillingbethatthatofF
the2
wassignificantinhavingthesequencesocalledfirstorderbondingmodel.ofMOI.e.theelectronInthe
configurationcaseofdichlorine,ofdifluorineandinis:fact1s
gall21s
theu
22s
heavierg21p
u

41p
halogensg
4.
too,thesequenceoffillingisthatoftheelementsuptonitrogeninthe2ndrowelements,i.e.thesocalled
secondorderorbitalsequence.Thisisshownheavierinthediagramshownatelements,theelectrontheright.
HenceconfigurationsforCl2
andtheare:1s
g

21s
Theu
21p
coloursu42s
g

21p
ofg
4.
thehalogens:fluorinepaleyellow,chlorineyellowgreen,brominedarkorangeandiodineas
purplevapourandasdarkpurplecrystalsareadirectresultoftheelectronicstructures.Absorptionofvisiblelight
occursbypromotionofelectronsfromthe1pwavelengthsg
4HOMOtotheofabsorbed2s

LUMO.light.Thecolourchangeingoingdownthegroupinvolvesaredshift,i.e.adroptolowerThis
correspondsdirectlytotheexpecteddecreaseinHOMOLUMOgapondescendingtheperiodictable,asthe
overlapthatleadstobondingdecreasesduetothelargersizesofthevalenceorbitals.
Notethebondenergiesofthedihalogens,showninTable6.1
Table6.1BondenergyindihalogensBondBondEnergy,kJmol1FCl2
159243Br193I
2

151
We see that the bond energy of difluorine is anomalously low. It is not surprising therefore that many of the
mechanisms for reaction of difluorine involve F radicals. The bond energy of chlorine issubstantiallylarger,and
only diiodine has a lower bond energy among thehalogensthandoesdifluorine.Thisweaknessifoftenattributed
to the extent of repulsion between the lone pairs on adjacent atoms due to the very short bond in difluorine.
However, molecular orbital theory provides a more cogent explanation: we know that pbondsforthe2ndperiod
elementsareparticularlyeffective.Indifluorine,strongnotonlythebondingpantibondaswellasthe1p
strongu
,butalsothepbondantibondingandweknow1p
alreadyg
orbitalsthatareantibondingquadruplyoccupied.alwaysmoreHencethanwecancelsmightexpectbondinga
overlap.
6.1.1IsolationoftheelementsTheelementsareproducedbyelectrolysisreactionofelectrochemistryCl
2

ofwiththechloralkalihalides(Br
cell2
andwereI
2discussed).(FThe2
andchemistryCl
2

),orbyandingreatdetailinChemistry2810,andIwillnotelaborateanyfurtheronthistopicnow.Itremainsa
vitalindustrialpreparativemethod,althoughtheoveralltonnageofelementalchlorineusageinindustryis
expectedtofallasincreasinglyalternatetechnologiesaredeveloped,e.g.forpreparationofpotablewatersupplies
andbleachingofpaperpulp.usingPureanelectrolysisF
2

wasfirstcell.preparedItwasbyonetheofFrenchmanthelastofHenrithecommonMoissanelementsin1886
in the periodic table to be isolated as the free element. Chemists had been aware of the existence of the element
from its compounds for many years beforehand, but the great reactivity of difluorine had prevented its isolation.
Moissan'scellconsistedofasmallplatinumU

Chemistry3810LectureNotesDr.R.T.BoerPage149
tube with fluorospar (mineral) stopperswhichallowedforplatinumelectrodesandsmalldeliverytubes.Originally
he tried pure HF as the electrolyte and source of fluoride ion, but he later realized that the electrolysisreactionis
catalysed by the presence ofalkalimetalfluorides.TheidealelectrolyteisKF.2HF.Thisreciperemainsthebasisof
the industrial preparation of fluorine to this day, with advances made only in the size and construction of the
electrolyticcells.
CH
3
2.5cm
Ptelectrodes
HF+KF

Schematic diagram of Henri Moissan's cell with gas delivery tubes

in 1886
The schematic diagram above shows the apparatus that Moissan built thatallowedhimtoproduceastreamof
fluorine gas emanating from one of the gas delivery tubes. Reactions were performed in small platinum crucibles
and deflagrating spoons containing other elements that were suspended in the gas stream. This diagram has been
illustrated in a contemporary etching, which is shown in the picture at the right. The caption signed by Henri
Moissanreads:Theexperimentthatpermittedtheisolationoffluorineforthefirsttimeonthe26thJune,1886.
ModernindustrialelectrolyticcellsfortheproductionofF
2

which he discovered F
29.5cm
PlatinumUtube
electrolyte
Clcoolant

areconstructedfrommildsteelusingasteelcathode
andacarbonanodeandagascollectorforthefluorinegasconstructedofmonel,analloyofcopperandnickelthat
showshighresistancetofluorineandishighlyprizedforthisreasoninallchemicalworkusingelementalfluorine.
enrichmentOneofprocedurethebigusesforofnuclearF
2

,usedinthe235Ufuels.NotethatCanadaisuniqueinusingapowergeneratingreactor
designbasedonnaturaluraniumfuel(thatis,fuelthatdoesnotrequireenrichment).Reactorsofallothercountries
usepartiallyenrichedfuel,thatisuraniumdioxidethathasanenhancedcontentofthe235Ucomparedtothe
major238Uisotope.Ofcourse,the235Uisalsousedinmanufacturingbombs.Hencethedifficultyin
distinguishingbetweenpeacefulandmilitaryusesofnuclearenergy.CountriesthatpurchaseCanadianbuilt
CANDUreactors,however,havenoexcuseatallforbuildingfuelenrichmentfacilities,whicharelargeindustrial
installationsthatareeasytodetectthroughgroundbasedandsatelliteintelligencesurveillance.

6.1.2 Special properties of uorine

Elemental fluorine is extremely reactive. When Moissan first isolated it, this reactivity immediately became
obvious. He observed: Phosphorus ignited in the presence of this gas, producing phosphorus fluoride. Sulphur

heated and melted rapidly.Carbonappearedtohavenoeffect.Fusedpotassiumchloridedisintegratedwhencold

and gaveoffchlorine.Finally,crystallisedsilicon,washedbynitricacidandhydrofluoricacid,ignitedoncontact
with thisgasandburntbriskly,producingsiliconfluoride.Theplatinoiridiumelectrodeformingthepositivepole
washeavilycorroded,whiletheplatinumelectrodeofthenegativepolewasintact.
Virtuallyeveryelementreactsdirectlywithelementalfluorine.Infactmostelementswillquiteliterallyburnin
afluorineatmosphere.However,somemetalsinbulkform,ifsufficientlypure,willoxidizeonthesurfaceinsucha
waythattheinitiallyformedfluoridelayerformsapassivecoatingofmetalfluorideonthesurface.Nickelisthe
bestatthisselfpassivationreaction.Inthisnickelresemblesthestabilizationofaluminumwithoxygen,forwhich
athinlayerofthemetaloxidepreventsfurtherreactionintheabsenceofaninitiator,suchasastrongacid.
Stainlesssteelwithahighnickelcontentandasmentionedabove,thealloyMonel,areallmaterialsthatcanbe
successfullyusedtohandleelementalfluorine.Neverthelessallworkwithelementalfluorineishazardousand
requiresgreatcautionandattentiontoeverydetailoftheexperiments.
remainsthepreparationofUF
6

Chemistry3810LectureNotesDr.R.T.BoerPage150
Specialvacuumlinesconstructedentirelyofmetalssuchasnickelandmonelarerequiredtoworkwith
elementalfluorine.Adiagramofsuchavacuumlineisshowninthefollowingfigure:
Legend for fluorine vacuum line: (A) monel valves, (B) nickel Utraps for the condensation of gases, (C) monel
pressure gauge, (D) nickel container for gas storage, (E) polytetrafluoroethylene reaction tube, (F) nickel reaction
vessel, (G) nickel canister filed with soda lime (a mixture of sodiumandcalciumhydroxides)forneutralizationof
reactiveHFwhichisacommonbyproductoffluorinationreactions.
In addition to these metals thatareselfpassivatingwithfluorine,theuseoffluorinatedhydrocarbonplasticsis
also very common in fluorine chemistry. Teflon is the common trade name for polytetrafluoroethylene, while the
more rigid KelF is polychlorotrifluoroethylene. Indeed, itwouldbefairtosaythatmodernfluorinechemistrywas
revolutionized by the wide spread availability of these specialty plastic products.Normallyglasscontainersmay
not be used in fluorine chemistry. As Moissan already observed, silica burns in fluorine. Furthermore, about any
hydrogencontaining compound, including water. HF is a common sideproduct HF strongly attacksglass.Hence
whenTeflonF
2

reactsandwithjustKelFarecommonlyusedasglassreplacementsinfluorinechemistry

6.2Halogenoxyacidsandoxoanions
The oxyacids and their conjugate salt anions, the oxoanions, of the halogensformthemostcompleteseriesof
any of the elements. Of course, they are only possible for chlorine, bromine and iodine, as fluorine is more
electronegative than oxygen. Chlorine and iodine form almost identicalseriesofthesecompounds,butbromineis
more difficult to ionize to the highest oxidation state (7), another consequence of the scandide contraction.
However,animportantdifferenceexistsfortheperiodicacid,whichhastheformulaH
5
OXYACIDSANDOXYANIONSOFCHLORINE
OX. ST.

+1 +3 +5 +7
ACIDS
hypochlorouschlorousHOCl..

..
.. ..
. .
H-O-Cl .. ..

. .
chloric.

. .. . .

perchloric

. . .. . . -


ANIONS
hypochloritechloritechlorateperchlorate

..
.. O
. . . . +

..
O
+2
O

.. ..
O

..
.
.
H-O-Cl ..

. .
..
. . . .
H-O-Cl-O . .

.. O
+3 . .
.. . - O
O O
O

IOHIOwhich46
,+ which2.

..
Cl

..

. .
.
Cl
O
. . Cl O
O

OClexists
correspondstotheformula
Hin2
O.basicHowever,media.
O

O
Thereisagreatdealperiodatetoisbestilllearned
IO
4

.
ClO
-
ClO
2
-
ClO
3
-
ClO
4
-

from a careful study of the halogen oxyacids and their anions, especially the series shown in the diagram for
chlorine. They are the most complete series of elementoxoanions known. Each is separated from the other by a
change of two oxidation numbers for the central atom. The+7stateishighlyreactive,andinparticularanhydrous
(pure) perchloric acid as well as many perchlorate salts are strong oxidizers. The explosive hazard ofperchlorates
wasdiscussedinChemistry2810.
TheinterconversionoftheseoxycompoundswasalsodiscussedinChemistry2810andrationalizedusing
electrochemicalbrownyellowgas),data.ClO
There2
(ayellowarealsogas)neutralandoxygenCl
2

O
7

(acompoundscolourlessofliquid).chlorineThoseinvolvedsuchinastheClO
redox2
thatcycles,belongincludingtoevenoxidation
Cl
2

O(a
statesofchlorineareoddelectroncompounds(freeradicals).Thisspeciesisproducedindiluteformonalarge
scaleasanoxidantforthebleachingofpaperpulp.Itisproducedbythereactionofsulfurdioxideonchloratesalts
bythereaction:

2ClO3(a q)+SO2(g)

a cid2ClO2(g)+

SO42 (aq)Thediagramthatfollowssummarizesthereactionsinvolvedintheinterconversionofthehalogen
oxyacids.Manyofthereactionsareeitherdisproportionationorcomproportionationreactions.

Chemistry3810LectureNotesDr.R.T.BoerPage151

6.3Chemistryofinterhalogencompounds
The halogens form derivatives of almost all the elements. Indeed, fluorine combines with all elements except
helium argon and neon. So common, and so important, are the element halides, that halogen derivatives are
discussed for all the other elements. Hence we will not deal with them in this section. An important class of
compounds exists, however, in which halogenelementsarebondedtoeachother.Suchcompounds(whichmaybe
neutral,anionicorcationic)areknownasinterhalogens.
InthelaboratoryforChemistry3810wedealwithinterhalogencompoundsinexperiment#10.Eachofthe
threecompoundsinthislaboratoryareexamplesofmonopositivewellasthecationiccomplexofI+withpyridine
ligands.Theseiodine,simplebutcompoundstheyarepreparedservetoasillustrateneutralthe(IBr),fascinating
anionic(ICl
chemical
2

),as
behaviouroftheinterhalogencompounds.ThestructuresoftheinterhalogensareaccuratelygivenbytheVSEPR
theoryasshownintheschemeatright,includingarareexampleofapentagonalbipyramidalmoleculeinIF
7

KNOWN INTERHALOGEN COMPOUNDS

Parent halogen

ClBrI.(Althoughtheevidenceisthatthiscompound
hasaslightlyirregularstructure,withinequivalentbondlengthsinthepentagonalplane.)Allarebasedon
S T R
ClF BrF IF
BrCl ICl
IBr

simplemonomericstructures,withtheheavierhalogenascentralatom,withthe
UCTsoleexceptionof"ICl
3
U R E S
Y
X X
X
Y
Y
Y
X
ClF
3

BrF
3
IF
3

",whichisactually
I
2
Cl
6

achlorinebridgeddimer,asfollows:
ClF
5
I
F
I
F F
F
BrF
5
IF
5
Cl Cl
Y F
IF
7 Cl
Cl
I
Cl
Cl
Y
Y
Y F
F

Thoseexampleswhichareunstablecompoundsareenclosedindashedboxes.Theydecomposebythe
followingreactions

5IF2I2+
IF5

ClF5ClF3+
F2

Chemistry3810LectureNotesDr.R.T.BoerPage152

5IF3I2+
3IF5
6.3.1 Synthetic routes to some interhalogens
IClandIBrcanbepreparedbymixingthehalogensinasuitablesolvent,asdoneinexperiment10:

I2+Cl2
2IClI2+Br2
2IBrButthisdoesnotworkforClF,whichispreparedby
thefollowingreaction:

2ClF3+HgCl2

100

40
atmC

4ClF+
HgF2
Note thehighpressuresinvolved.IhaveperformedthisreactionwheninvolvedinaresearchprojectattheFree
University of Berlin. We employed stainless steelautoclaves(pressurereactors)whichcouldbeheatedandshaken
in remote chambers in an autoclave roomtoprotectfromexplosionscausedbyaruptureofthepressurereliefdisks
that could occur if the pressure built up to too high a value. Note again the use of mercury (we saw this element
earlier in the transmetallation synthesis of many element organometallics) it is an extremely versatile element in
chemicalsynthesis.
Theremaininghalogenfluoridesaremostlypreparedbydirectinteractionoftheelements,asshownbythe
followingexamplesbutnotethepreparativeroutetoIF
7

Br2+3F2
2BrF3(200C)I2+5F22IF5(25C)PdI2+8F2PdF2+
2 IF 7 (200 C ) 6.3.2 Halogen and
interhalogen anions
The simple anions are perhapsthemostcommonlyencounteredforallthehalogenelements.Closelyrelatedto
the halogen anions F, Cl, Br and I arethemolecularionsknownasthepseudohalides.Theseareanimportant
class of mononegative anions that mimic the chemistry of the halides. In a few cases, the corresponding neutral
dimers also exist, i.e.whatisoftencalledapseudohalogen.Somecommonexamplesofthisclassofcompoundsare
inthefollowingtable.
PseudohalidePseudohalogen0
12

AcidpK
a

*CNcyanide

E(red.)/V
NCCNcyanogen
+0.27HCN
hydrogencyanide
9.2
SCNthiocyanate
NCSSCNdithiocyanogen
+0.77HCNS
hydrogenisothiocyanate
1.9
OCNcyanate
HCNOisocyanicacid
3.5
CNOfulminate
HCNOfulminicacidNNNazide
HNNNhydrazoicacid
4.92
*A.AlbertaandE.R.Serjeant,Thedeterminationofionizationconstants,London(1984).

known,Thebutmosttrichloridecommonisexamplesmuchlessofstableaninterhalogenandisrarelyanions
encountered.ismostdefinitelyW hileIwasthetriiodideapostdoctoralion,I3
.researcherThetribromideattheUniversityionisalso
of Guelph, however, I was involved on a project in which a student named Robert Reed isolated such an anion
during a chlorination reaction. Indications ofsomethingunusualaboutthisstructurewasthelowC,H,Nanalytical
data, and the tendency for the crystals to decompose with the smell of halogens. Fresh crystals were a beautiful
rosered colour, but on standing they tended to decolourize. The answer tothepuzzlecamefromtheXraycrystal
structure,whichclearlyshowsthepresenceofanunsymmetricaltrichlorideioninthecrystallattice.

Chemistry3810LectureNotesDr.R.T.BoerPage153
LegendforthetrichloridereactionandstructureInthisreactionwewereoxidizingaweakcrossringsulfursulfur
bondwithmolecularchlorine.Cl+wasaddedtothesulfurinareactionreminiscentofthecyclicbromoniumionof
organicchemistry(additiontoanalkenebymolecularbromine).ThecounterionshouldthenhavebeenCl.
Instead,weincorporatedasecondmoleculeofchlorineintothelattice,whichcombinedwiththeexampleofCl
antoOakformRidgeCl
3

.ThermalThelowerpictureisElipsoidPrograman
output in which 3D elipses are drawntoindicatetheregionofspaceinwhich30%oftheelectrondensityofeach
atom is found, as a result of molecular vibrations within the crystalline lattice. R.T. Boer, et. al. J. Chem. Soc.,
Chem.Commun.(1985)655
Thetendencyoftrihalideanionstostructurallydistortiswelldocumented,andisanindicationofthevery
polarizableelectronrichbondinginthesesystems.Inclassicalwetanalyticalchemistry,triiodideiscommonly
usedasanessentiallyawaytosolubilisethemoleculariodinemoleculeinthehighlypolarsolventwater:
I
2

equivalent,
I2(s

)+ I( aq)I3( aq)Wewillconsidertheuniquebonding
situationintrihalideanionsbelow.Foriodine,itisalsopossibletogobeyondtriiodideandformpolyiodide
anions.Thestructuresofthesespeciespersistonlyinthesolidstate,andcriticallydependontheidentityofthe
counterions.Somestructuresthathavebeendeterminedforpolyiodideanionsareshowninthefollowingdiagram.
Somepolyiodidesaltsexhibitelectricalconductivity,whichisthoughttocomefromelectron(orhole)
hoppingthroughachainofiodineatomsinthesolidstate.Thismechanismresemblesthatofprotonmigration
throughahydrogenbonded

Chemistry3810LectureNotesDr.R.T.BoerPage154
array of molecules, either in the solid or in a liquid like water. It can be diagramed by the picture shownatright,
and means that I can pass rapidly through the matrix, but that the emerging iodide is not the same as theiodide
thatenteredattheotherendoftheelectricalcircuit.
Finally,intheChemistry3810laboratory,youalsohavetheopportunitytoprepareamixedhalogeniodine
withtwopolyanion,chlorideanions,ICl
2

,givenwhichthatmayinbethoughtofasacomplexofmonopositivethiscasechlorineismoreelectronegative
thaniodine.

6.3.3 Halogen and interhalogen cations

Cationsofhalogenscanformunderstronglyoxidizingconditions.Forexample,iodineisoxidizedinfuming
sulfuricacidtotheblueparamagneticdiiodoniumcation,I
2

+.

I2

SO3/
H2SO4

I2+ Extensiveworkonthedevelopmentofthe
chemistryoftheiodinecationswasdoneinCanadaintheresearchlabofProf.JackPassmoreattheUniversityof
NewBrunswickinFredericton.Amongthestructureshehasobtainedarethefollowing:
I
I
F
F
F
I
I
I I I
I F
F
Sb
F I
5
Cl
+
F
F
+ I

3
+ F
2

Cl+
Thelastexamplewiththecorrespondingreagentsknownasisthatofamixedhalidecation,neutralsuperacids.
chlorinefluorideSuperacidsareextremelyClF
3

.whichisformedbytheinteractionofthepowerfulLewisChemistryofthistypeisdependentonthepropertiesof
aacidclassSbFof5
strongly acidic, nonaqueous solutions of which fuming
sulfuric acid was the original inspiration. A superacid normally contains a strong Brnsted acid as well as a
powerfulLewisacid.Infumingsulfuric,theformerissuppliedbyH
2

SO
4

,whileSO
3

functionsasthelatter.

6.3.4 Bonding in interhalogens

We have spoken at length in this course aboutthebondinginelectrondeficientcompoundssuchastheboron
hydrides. A general theme for such compounds is the tendency to formdimersorclusterswhichcanbethoughtof
as measures of desperation: if the elements cannot gain sufficient electrons they somehow have to make to with
what they have. The halogen and noble gas compounds we are now considering are, however, examples of
(extreme) electron richness. Remember that in the dihalogens themselves, there is only a single empty orbital
capableofacceptingelectrons,the2s
u

*
orbital. Yet halogens are noted charge acceptors, forming socalled charge transfer complexes with awidevariety
of electron donors. This tendency canonlybeexplainedbythehighelectronegativityofthehalogens,resultingin
thefactthateventhehighestvalencemolecularorbitalisrelativelylowlyinginenergy.
(A)BondinginICl
Asourfirstexampleofbondinginelectronrichhalogens,considerthesimpleinterhalogencompoundICl.The
UVPESofthisinterhalogenisshownatright,andaPM3MOcalculationresults(partial)attheleft.
EnergyLevelsofupperMOs(orbitalpicturesfor3s,1pand2p.)

Chemistry3810LectureNotesDr.R.T.BoerPage155
Thephotoelectronspectrumiscomplicatedbythepresenceofspinorbitcoupling,whichhastheeffectof
splittingtheionizationfromthe2plevelintotwopeaks.Wetaketheaverageofthesetwopeaksastheionization
energy.AgreementtothePM3methodisreasonableforthismolecule.Aboveall,UVPESestablishesthatthelevel
orderingisthatshowninthecalculation,i.e.thattheelectronconfigurationis1s22s23s21p22p2ratherthanthe
orderobservedfortheheavierdihalogensthemselveswhichfollowthesecondorderorbitalsequence.You
shouldconfirmthisbybuildingthefullMOdiagramforIClfromtheconstituentatomicorbitals.
(B)TriiodideanionW hatstructureHowever,VESPRrationaleI
3

isalinearisexpectedmolecule.ofI3That?ofmolecularstructure:
Thisisanimportantquestion,becausemost3atommoleculesareindeedbent.isbecauseitisbasedonthetrigonal
bipyramidalelectronarrangemeninthe
.. ..
. . .. .. I I .. .. I
. .

..TotreatthebondinginasimpleasitsprincipalbasisAOinbondingontopaperfashion,wecanmakethe
approximationthateachitsneighbours.WecantestthishypothesislaterbyaiodineusesafullMOtreatmentpz
orbitalusingHyperChem.Nowconsiderwhatthisarrangementshouldlooklike,andwhatitssymmetryproperties
willbe.Thereisanobviouslogicallinkorbitalswillthenbe:
tooursimpleH
3

structuresdoneatthebeginningofthecourse.Thetopologyofthethreep
z

antibonding

bondingHowever,unlikethetrihydrogensystemwhereweuseds
orbitals,thebondingandantibondingcombinationoforbitalsherewillhaves
u
nonbonding

inwhichwecombinethetwosymmetry,terminalwhileiodidetheanionsnonbondingtothecentralhass
gI+symmetry!ionisthenexpectedThecorrespondingtobe:
energyleveldiagram
I3
2I2
u

1
g

1
1
u

Fillingthissimpleschemeorbitals.W hatthenisthebondwiththefouravailableorder?Thereareonlyelectrons
twoelectronsfillsthebutbondingthreebonded1s
u

andatoms.thenonbondingTheoverall1s
bondg
molecularorderisthen1andtheorderperbondis.Thisisthenanotherexampleofadelocalized(3c,2e)bond,
albeitofadifferenttypefromthatobservedinthebentbondsinTheeasewithwhichtriiodideanionscanB
be2
H
distorted6
.Suchbondsareextremelycommonamongthehalogensandnoblegases.
bytheirenvironmentcanberationalizedbysuchweakbonding.
WecannowrationalizethediagramorbitalresultsforH
3.inRememberthatalineargeometry.linearitisH
Ofgeometry3+ whichcourse,isinpredictedinI
3theusingtruetotheseelectronicbetriangular,simplestructureMObutarguments,theofpresencetriiodide
justofasanion,theweelectronsdidtherewithareinatheWalshmany1s
u

additionalelectronsofpsymmetrythatalsocontributetothelineargeometry.AtthePM3leveloftheory,
amazingly,apictureveryreminiscentoftheabovesimplemindedbondingpicturedevelops.

Chemistry3810LectureNotesDr.R.T.BoerPage156
ThefullMOenergyleveldiagramfortriiodideanioninPM3is:
MOpicturesforalltheorbitalsareshownnext:
1s
g

:
2s
g

:
3s
g

:
Itisveryclearthatsimplepicturedevelopedtheabove.orbitalsAmazing1s
u

(+1.0eV)correspondalmostdirectlytothetoseeistheextremelysmallinvolvementoftheatomicsorbitals,
whichIcanonlyexplainbythelargeIIdistancesof2.73?inthegeometryoptimizedstructure,i.e.toofarapart
foreffectivessoverlap,butbettersuitedtolinearppoverlap.Thechargedistributionisalsointeresting,with
+0.27onthecentralatom,and0.63oneachterminalatom.
Finally, note that there is nothing atallintheMOdiagramtocorrespondtothethreelonepairssurrounding
the central atom in the VSEPR structure! Indeed, there are many suggestions from calculation that the VSEPR
theory is not a true theory of chemical bonding and structure. It is a very reliable method that returns correct
structures,butshouldnotbeaccordedagreatdealofveracitybeyondthisutilitarianaspect.
The remaining MOs in triiodide (and remember that I have onlyprovidedapictureforoneofeveryporbital)
correspond to the many lone pairs. In all thereare12MOsofwhich11arefilled.Ofthese,threecorrespondtothe
atomicsorbitals,andsixtolonepairsofpsymmetry.
1s
u

:
1p
g

:
2p
u

:
(8.8eV),2s
g

(6.3eV)and3s

1p
u

:
2s
u

:
3s
u

Chemistry3810LectureNotesDr.R.T.BoerPage157
(C)Bondinginahypervalentcompound:theexampleofBrF
5

ThestructureofBrF
5

F 1.68
82
F
Br
F
F
F
1.75 - 1.82
This is quite a remarkable structure. First of all, the atoms in the equatorial plane areactuallybentuptowardsthe
axidal fluorine, and not away from them. VSEPRrationalizesthisresultbypointingtoalonepairontheBrthat
is largeandneedsmoreaxialspace.This,saysthetheory,causestheequatorialatomstobendupoutoftheplane.
Note also that the axial BrF bond is considerablyshorterthanthefoursuchbondstotheequatorialplanewhich
are around 1.8?inlength.ConsiderfirstadescriptionofthisstructureusingelectronpreciseLewisstructures.Such
structures must invoke socalled nobond resonance to describethebondinginthiscompound.Rememberthatthe
true Lewis diagram isahybridofallthecontributingstructures,sothattheabsenceofabondinanyoneofthefive
isomersdoesnotimplythatabondisactuallybroken!
F
Br

is:
F
F
Br
Br
F
F
F
Br
Br F
F
F
F
F

F F
F
F
F

ThefullMOdiagramofBrF
5
F
F
F
F
F +
+
+
+
F F
F F

is extremely complex, and we will restrict ourselves in thiscoursetoasimplified

on paper MO diagram that uses only slike functions for the fluorineatoms.ThiscanbecalculatedinHyperChem
usingamodelligandsBrH
functions.5
moleculeandbyemployingtheextendedHckelMOmethod.FirstweneedsuitableSAOsforthefiveTheseare
notprovidedbythebook,sowemustmakeourown.Thesearemodeledontheonesinthebookforsquareplanar
geometry,butinvolveadifferentsettingofthemoleculew.r.t.theCartesiancoordinates.Hereissuchasetof
SAOs:

e a
1
C C

a
1

b
2Inthispointgroup,ase.Rememberingthat
theatomicfluorineisorbitalsconsiderablytransformmoreas:electronegativesandp
z

boththantransformbromine,asa
1we,whilearereadyp
x

andtop

combiney
transformtheasasetcentralatomAOandtheligandSAOs.Thisisdoneonthefollowingpage.
Nowthereareseveralpointstoconsiderinthisbondingscheme.Notefirstofallthatthereisnob
2

componenton
bromine.approximation,Hencethethe2a
molecular1
orbitalisb
almost2
MOisentirelyattheexactdedicatedenergytobondingoftheligandintheorbitalsaxialdirection,andistotally
asshownnonbonding.intheHyperChem
Toafirst
1a
1

3a
1

plots.bondorderBycontrast,fortheaxial1a1
anddirection1earelargelybondingintheequatorialplane,andisessentially1,whilefortheequatorialdirection
3a1
isisoverallalmost3,nonbonding.oronly0.75HencetheperBrFbond!Thisthenrationalizestheobserved
muchlongerbondlengthsfortheequatorialbondscomparedtotheaxialbond.InthefullMOpicture,itisalso
possiblethatthereisapcomponenttotheaxialbondsthatisnotavailabletotheequatorialset.Finally,indetailed
MOcalculationsonthissystemithasbeenshownthatthesmallFBrFbondanglesdirection,betweenandthis
thehelpsaxialtoandrationalizeequatorialthesesitesmallenablesbondtheangles.3a
1

MORemembertogainasmallthatdegreeofbondingcharacterintheaxialintheVSEPRexplanation,the
upwardsbendingofthesebondsisexplainedbythelargelonepairbelowtheBrF
4

plane.
1e2a
1

1b
2

Chemistry3810LectureNotesDr.R.T.BoerPage158