Perspective

NatureChemistry1 ,443-449(2009) 1 Publishedonline:24August2009|doi:10.1038/nchem.327

S u b j e c t C a t e g o r i e s : G e n e r a l c h e m i s t r y | T h e o r e t i c a l c h e m i s t r y

Charge-shift bonding and its manifestations in chemistry

SasonShaik ,DavidDanovich ,WeiWu &PhilippeC.Hiberty
1 1 1 1 2 2 3 3

E l e c t r o n - p a i r b o n d i n g i s a c e n t r a l c h e m i c a l p a r a d i g m . H e r e , w e s h o w t h a t a l o n g s i d e t h e t w o c l a s s i c a l c o v a l e n t a n d i o n i c b o n d f a m i l i e s , t h e r e e x i s t s a c l a s s o f c h a r g e - s h i f t ( C S ) b o n d s w h e r e i n t h e e l e c t r o n - p a i r f l u c t u a t i o n h a s t h e d o m i n a n t r o l e . C h a r g e - s h i f t b o n d i n g s h o w s l a r g e c o v a l e n t i o n i c r e s o n a n c e i n t e r a c t i o n e n e r g y , a n d d e p l e t e d c h a r g e d e n s i t i e s , a n d f e a t u r e s t y p i c a l t o r e p u l s i v e i n t e r a c t i o n s , a l b e i t t h e b o n d i t s e l f m a y w e l l b e s t r o n g . T h i s b o n d i n g t y p e i s r o o t e d i n a m e c h a n i s m w h e r e b y t h e b o n d a c h i e v e s e q u i l i b r i u m d e fi n e d b y t h e v i r i a l r a t i o . T h e C S b o n d i n g t e r r i t o r y i n v o l v e s , f o r e x a m p l e , h o m o p o l a r b o n d s o f c o m p a c t e l e c t r o n e g a t i v ea n d / o r l o n e - p a i r - r i c h e l e m e n t s , h e t e r o p o l a r b o n d s o f t h e s e e l e m e n t s a m o n g t h e m s e l v e s a n d w i t h o t h e r a t o m s ( f o r e x a m p l e , t h e m e t a l l o i d s , s u c h a s s i l i c o n a n d g e r m a n i u m ) , h y p e r c o o r d i n a t e d m o l e c u l e s , a n d b o n d s w h o s e c o v a l e n t c o m p o n e n t s a r e w e a k e n e d b y e x c h a n g e - r e p u l s i o n s t r a i n ( a s i n [ 1 . 1 . 1 ] p r o p e l l a n e ) . H e r e , w e d i s c u s s e x p e r i m e n t a l m a n i f e s t a t i o n s o f C S b o n d i n g i n c h e m i s t r y , a n d o u t l i n e n e w d i r e c t i o n s d e m o n s t r a t i n g t h e p o r t a b i l i t y o f t h e n e w c o n c e p t .

Thereareprobablyonlyahandfulofconceptsthatareasfundamentalandcentraltochemistryasthatoftheelectron-pairbond.Eversincetheingenious hypothesisofLewis ,followedbypioneeringworkofHeitlerandLondon ,ontheoriginsofelectron-pairbonding,andthecolossalintellectualconstructof Pauling ,electron-pairbondinghasbeentraditionallyclassifiedintotwomajorfamilies

3 3 3 4,,5 3,,4 5 1 1 2 2

.Oneisthefamilyofcovalentandpolar-covalentbonds,in

whichthebondingarisespredominantlyfromstabilizationduetothespin-pairinginthecovalentstructureofthebond.Thesecondfamilyinvolvestheionic bonds,inwhichthebondingarisesprimarilyfromtheelectrostaticstabilizationofthetwooppositelychargedfragments.Hence,basedonthistraditional classification,thebondingtypecanbecharacterizedbyknowledgeofthestaticelectronicdistributioninthebond,using,forexample,electronegativities,or electron-densitypopulationanalysesprovidedinstandardquantumchemicalcalculations.However,thesetraditionalclassesofbondingcannotdescribe manyintriguingfeaturesofbonds,ofwhichwementiontwoexamples,oneregarding'ionic'bonds,theotherregarding'covalent'bonds: Thus,forexample,thebondsH Si

3 +0.85 -0.85

,Li

+0.94 -0.94

andNa

+0.91

Cl

-0.91

,wherethesuperscriptednumbercorrespondstogroupcharges,allhave'ionic'
+ + + 8 9,,1 0 8,,9 10

chargedistribution(determinedbycharge-densityintegrations)

5 6,,7 5,,6 7

.But,whereasLi F andNa Cl behavechemicallyasgenuineionicbonds,the'Si X ' .

bonds(X =halide,perchlorate,andotherelectronegativegroups)behavechemicallyascovalentbonds
2 2

AnotherstrikingexampleisthedifferencebetweenH andF ;twohomonuclearbondsthatbyallcriteriashouldbeclassifiedascovalentbonds,butexhibit fundamentaldifferences.Considertheenergycurves(F i g . 1 )ofthetwobondscalculatedrecently F

5 11 12 5,,1 1,,1 2

.F i g u r e 1 a showsthattheHHbondisindeed F

covalent;itscovalentstructureaccountsformostofthebondingenergy(relativetothe'exact'curve).Bycontrast,fortheFFbondinF i g . 1 b ,thecovalent F structureisentirelyrepulsive,andwhatdeterminesthebondingenergyandtheequilibriumdistanceisthecovalentionicmixing.Thismixingleadstoa resonanceenergystabilization,whichwehavetermedthe'charge-shiftresonanceenergy'(RE verydifferent;whereastheHHbondisatruecovalentbond,theFFbondisaCSbond above-mentionedSiXbondsarealsoCSbonds,andtheoriginalpapers

5 12 13 14 5,,1 2,,1 3,,1 4 5 12 5,,1 2 CS

).Thus,despitetheirapparentsimilarity,thetwobondsare
CS

thatiscompletelydeterminedbytheRE

quantity.The

includeafewmorepuzzlingexamplesthatcounterthetraditional .Thefeaturesofthisbondfamily,itsterritory

classification.Indeed,ourworkoverthepastdecadedemonstratesthatCSbondingconstitutesalargeanddistinctclassofbondingalongsidethetwo classicalfamilies,andthatitpossessesuniquechemicalandphysicalsignatures andchemicalmanifestations,arediscussedinthisPerspective.

5 11 12 13 14 15 16 17 18 5,,1 1,,1 2,,1 3,,1 4,,1 5,,1 6,,1 7,,1 8

F i g u r e 1 : V a l e n c e b o n d c o m p u t e d e n e r g i e s ( E ) a s f u n c t i o n s o f t h e i n t e r a t o m i c d i s t a n c e s ( R ) f o r s o m e b o n d s .

TheprincipalVBstructureisshowninblueandtheexactgroundstateinred;thelatteristhecovalentioniclinear combinationdefinedbyeq.(1).a f ,TheprincipalVBstructureisthecovalentoneforHH(a ),FF(b ),BH(c )andFH(d ), a a b c d andtheioniconeforNaF(e )andNaCl(ff).Theenergydifferencebetweentheexact(red)curveandthedominant e VB-structurecurve(blue),attheminimumdistanceofthebond,isthecharge-shiftresonanceenergy.Partsa andb are a b reproducedwithpermissionfromref.5 ,2005Wiley. 5 F u l l s i z e i m a g e ( 6 0 K B ) T h e o r e t i c a l c h a r a c t e r i z a t i o n o f b o n d t y p e s Theemergenceofthreebondingfamiliescovalent,ionicandnowCSwasoriginallyderivedfrommodernvalencebond(VB)calculations expressedineq.(1),theVBwavefunction( )ofabondAXiscomputedasacombinationofthecovalentform (A X )and '
+ ion cov 12 12

.As
ion

(A X),andtwoionicforms,

(A X ):

- +

Thebond-dissociationenergy(D )istheenergyofthiscovalentionicwavefunctionrelativetotheseparatefragments(A andX )attheirrelaxedgeometric

e

andelectronicstructures.Thus,D hastwocontributions;onecomesfromthebondingenergyoftheprincipalVBstructure,andtheotherfromRE
e

CS

dueto is

thecovalentionicmixing.TheprincipalVBstructureistheonehavingthelowestenergy,andhencealsothelargestcoefficientamongthethreestructures ineq.(1).ItscontributiontothebondingenergyisreferredtoasD
cov

orD

ion

,whereinthesubscriptspecifiesthedominantVBstructure.Inallcases,RE
ion

CS

determinedbyreferencetotheprincipalVBstructure,forexample,

cov

inF i g . 1 a d ,or F

(F i g . 1 e , f ). F
cov

ThesequantitiescharacterizethebondingtypeascanbegleanedfromF i g . 1 .ThustheprincipalVBstructureforbothHHandBHis F quantityissmallandmuchlesssignificantthanthelargeD

cov

,theRE

CS

(F i g . 1 a , c );inaccordancewiththis,thesebondsareclassicalandpolar-covalenttypes, F
cov

respectively.Bycontrast,FH(F i g . 1 d )showsaweaklyboundprincipalstructure F extremecaseistheFFbond(F i g . 1 b )inwhichtheprincipalstructure F ,andtheRE

cov

,whereasthemajorcontributiontothebondcomesfromRE
cov

CS

.An

isnotevenbonded,thatis,D

isnegative,whereasRE

CS

isevenlargerthan

thetotalbondingenergy.Inagreementwiththis,FHandFFarebothCSbonds.Finally,inNaFandNaCl(F i g . 1 e , f )theprincipalVBstructureisnow F
ion CS

quantityisaminorcontributor,makingbothclassicalionicbonds,wheremostofthebondingenergyarisesfromtheionicstructure.
19 19

Analternativewaytocharacterizebondinguseselectron-densitytheories,suchasatomsinmolecules(AIM) interactionswithinmolecules
2 1,,2 2 21 22

andelectronlocalizationfunction(ELF)

20 20

TheAIMparameterscanbeeithercalculatedorderivedfromdensitydeterminedexperimentally,andareusedbyexperimentalchemiststocharacterize .Inthistheory,abondisgenerallycharacterizedbyabondpath,whichdefinesamaximumdensitypathconnectingthe
c c 2

bondedatoms.Thepointofthepathatwhichthedensityisataminimumiscalledthebondcriticalpoint(BCP),andthevaluesofthedensity, (r ),wherer isthelocusofthebondcriticalpointandtheLaplacian,

c

(r ),atthispointarecharacteristicofthebondingtype.AccordingtoAIM,aclassicalcovalent
c 2

bondistypifiedbyasignificant (r )value,andalargenegative Laplacian. TheLaplacianisespeciallytelling local-virialtheoremexpression:

1 9,,2 3 19 23

(r ).Bycontrast,closed-shellinteractions,whichexperiencePaulirepulsions(also
c

knownasoverlaprepulsionorexchangerepulsion),asinionicbonds,ortheHe---Heinteraction,havecharacteristicallyasmallcriticaldensityandapositive

,asitisconnectedtothekineticandpotentialenergydensitiesatBCP,G(r )andV(r ),respectively,bythefollowing

c c

Thus,anegativeLaplacianmeansthatthebondingregionisdominatedbytheloweringofthepotentialenergy,whereasapositiveLaplacianmeansthatthe interactionistypifiedbyexcesskineticenergy,andhenceisrepulsive. TheELFapproachisanothertopologicalmethod,whichusesafunctionrelatedtothePaulirepulsiontocarryoutapartitionofthemolecularspaceinto basinsofattractorsthatcorrespondtothevolumesoccupiedbycoreinnershells,bondsandlonepairs.AsintheLewismodel,avalencebasinmayeither belongtoasingleatomicshellorbesharedbyseveral.Inthefirstcase,thebasiniscalledmonosynapticandcorrespondstoalone-pairregion,andinthe secondcaseitispolysynaptic,andspecificallybisynapticforatwo-centrebond.Thebasinpopulation, ,anditsvariance,

2 2

,arecalculatedbyintegrating

theone-electronandthepairdensityoverthevolumesofthecorrespondingbasins.Foraclassicalcovalentbond,thebasinisdisynaptic,itspopulationis closeto2.0,andthevarianceissignificantlysmallerthanthepopulation,whereasaclassicalionicbondsuchasNaClhasonlycoreandmonosynaptic basins

5 20 24 5,,2 0,,2 4

.
5 11 12 13 14 15 16 17 18 5,,1 1,,1 2,,1 3,,1 4,,1 5,,1 6,,1 7,,1 8

Toprovideaglobalpictureofthevariouscategoriesofbonds,27bonds

arepresentedinT a b l e 1 ,andareorganizedinto T
18 18

threegroups,labelledIIII.ThefirstgroupinvolveshomonuclearbondsfromHHtothe'inverted'CCbondin[1.1.1]propellane(seeF i g . 2 c ) F
Nature Chemistry

.GroupsII

andIIIinvolveheteronuclearbonds,fromCHtoSiF.EachbondischaracterizedbyVBproperties;theweightoftheprincipalVBstructure( bondingenergyofthatstructure(D (%RE

CS cov

cov

ion

),the

,D

ion

)followedbythefullbond-dissociationenergy(D ),andRE
e CS e

CS

,followedbytherelativeresonanceenergy
2

),whichisthepercentageratioofRE

toD .ForsomeofthebondsweshowAIM-derivedquantities, and

2 cov

aswellastheLaplacian
2 res

componentsintheBCPforbondingduetotheprincipalstructureofthebond(

or

ion

),andthecovalentionicresonance(

11 11

F i g u r e 2 : S o m e E L F r e p r e s e n t a t i o n s o f e l e c t r o n d e n s i t y i n a f e w t y p i c a l c a s e s . a ,TheELFdisynapticbasin forH CCH .b ,Themonosynapticbasins fortheFFbond.c ,Disynapticbasinsforthewing b c

3 3 5 5 5 5

bondsof[1.1.1]propellane,andtwomonosynapticbasinsforthecentralinvertedbond characterizedbyRE
CS

26 26

.Thenatureofeachbondisfurther

,theELFbasinpopulation ,anditsvariance
2
-1

2 2

,thedensity atthebondcriticalpointandthe
-3 -5 ,Laplaciansinea ).ForH CCH andFF,the 0 0 3 3

correspondingLaplacian
25 25

(energiesareinkcalmol ,densitiesinea

ELFandAIMparametersaretakenfromRefs5 and1 1 ,respectively.For[1.1.1]propellane,theAIMparametersare 5 1 experimentalvalues (averagedforthewingbonds)fromthestudyofasubstituted[1.1.1]propellanederivative.TheELF drawingsina andb arereproducedwithpermissionfromref.5 ,2005Wiley.TheELFdrawingincisreproducedwith a b 5 permissionfromref.2 6 ,2007Wiley. 2 F u l l s i z e i m a g e ( 3 9 K B )

T a b l e 1 : A c o l l e c t i o n o f b o n d s w i t h t h e i r V B a n d A I M p r o p e r t i e s : g r o u p I c o r r e s p o n d s t o h o m o n u c l e a r c o v a l e n t a n d C S b o n d s , I I t o h e t e r o n u c l e a r c o v a l e n t a n d C S b o n d s , a n d I I I t o i o n i c b o n d s .

F u l l t a b l e LetusfirstinspectthehomonuclearbondsinpartIofT a b l e 1 ,whichbyalldefinitionscouldnotpossessstaticbond-ionicities.Thebondenergiesinentries T 14aredominatedbythecovalentcomponent,withRE bondingenergydominatedbyRE

CS CS

beingtheminorbondingcontribution(<50%).Bycontrast,thebondsinentries610,allhavea
cov

(>100%),whereasthecovalentstructureisrepulsive(D

<0).TheNNbond,entry5,isaborderlinecase,withRE

CS

accountingfor66.6%ofthetotalbondingenergy.LeavingasidetheweakNaNaandLiLibondsforwhichallAIMparametersareclosetozero,thereisan excellentcorrelationbetweentheRE
CS

quantitiesandtheAIMparameters,especiallywithinthesamerowoftheperiodictable.Thus,fromCCtoFF
2 res

(entries47),theresonancecomponentoftheLaplacian( component(
2 cov 2

)ismoreandmorenegative,inagreementwiththeincreaseofRE

CS

,whereasthecovalent

)goesfromnegativetopositivevalues,inagreementwiththerepulsivenatureofthecovalentstructureinCSbonds.Asaresult,the
2 25 25

totalLaplacian boththeRE
CS

islargeandnegativeforclassicallycovalentbondsandeitherasmallnegativeorapositivevalueforCSbonds.Notethat,accordingto values ,the[1.1.1]propellanemoleculeembodiesthetwocategoriesofbonds,classicallycovalentfor

andtheexperimentallyderived

thewingbonds(entry11)andCSbondforthe'inverted'centralbond(entry10). ThesamedistinctionbetweenthecovalentandCSbondgroupswasrecentlyshowntoemergefromELFanalysis .Thus,bondssuchasHH,CCand LiLi,werefoundtopossessdisynapticbasinswithapopulationcloseto2.0andsmallvariances,whereasbondssuchasFF,ClCl,OO,BrBr,NNand theinvertedCCbondof[1.1.1]propellanepossesssmallbasinpopulations statisticaltheoryofthebasinpopulations,thecovariances

5 5 5 27 5,,2 7 26 26 5 5

( 1.0),withvariancesandcovariancesaslargeasthepopulation.Inthe

gaugedirectlythecovalentionicfluctuationsand,usually,arelargefortheCSbondsand

smallforthecovalentbonds .However,asthecovariancesshowsimilartrendstothevariancesweonlyshowthelatterinthefollowingdiscussion.These trendsaredemonstratedinF i g . 2 ,whichshowsthemolecularbasinsforH CCH ,FFandCCin[1.1.1]propellane,alongsidetheirVBandAIM F

3 3

properties.Furthermore,itisseeninF i g . 2 b , c thatthedisynapticbasinsofFFandtheinvertedCCbondofpropellaneareinfacttwomonosynaptic F basins,muchlikedissociatedbonds.Thus,thethreemethodsofdiagnosingbondingagreeontheclassificationofhomonuclearbondsintotwofamilies,and theVBmethodbringsadditionalenergeticinsightthathighlightsthedominantroleoftheRE

CS

energyintheCSbondgroup.

TurningbacktoheteropolarbondsinpartIIinT a b l e 1 ,wenotethefollowingtrends.WhereasthecovalentVBstructureistheprincipaloneforallthese T bonds,thebondsstillfallintotwodistinctgroups.Specifically,entries1215belongtotheclassicalpolarcovalentbondfamilybasedontheir%RE

CS

,which

iswellbelow50%.Bycontrast,thebondsinentries1622allhaveweaklybondedcovalentstructures,andlargeRE contributiontobonding(D ),withsmallRE

CS

exceeding50%andinsomecases

>100%.InpartIIIofT a b l e 1 theprincipalVBstructureofallbondsisionic.Thebondingenergiesinentries2326arealldominatedbytheelectrostatic T
ion CS

contributions.Theseareclassicalionicbonds.Finally,theSiFbondinentry27isspecial:itsprincipalVB
CS

structureisionic;itsstaticionicityislarge,butitsRE
8 8

issignificant,muchlargerthanthatintheclassicalionicbondsinIII.Valencebondtheorypredicts
14 14

5 5

thatthisbondwillbeverydifferentfromionicbonds.Asalreadyalludedtoabove,theSiXbondsbehaveasthoughtheywerecovalentdespitetheirlarge ionicity .Here,inIIandIII,thesebondsandtheirheavieranaloguesareclearlymarkedeitherasCSbonds(SiCl,GeCl) character(SiF) . TheAIManalysisoftheheteropolarbondsinIIdoesnotdistinguishbetweenthecovalentandCSbonds,buttheLaplaciancomponentsintheBCPshow thattheCSbondshavemorepronounced

5 5 2 res 5 5

orasbondswithalargeCS

values

11 11

comparedwiththeclassicalcovalentbonds,inlinewiththedominantRE

CS

quantity.

Interestingly,theELFanalysis ofthesebondsshowsbettertheirCSnature;allhavingdepleteddisynapticbasins( =0.861.22)withhighvariances (0.640.68),andthecaseofSiFisverysimilartoFF,withameagrepopulation(0.27)andavariance(0.24)thatisequaltothepopulation.Finally,theAIM analysisoftheclassicalionicbondsinIII(ref.1 1 )showstheexpectedcharacteristicsfromclosed-shellinteractions;allhavepositiveLaplaciansthatare 1 dominatedbytheioniccomponent, monosynapticbasins. Insummary,CSbondingemergesasadistinctclassalongsidethecovalentandionicbonds.InVBtheory typifiedbylargeRE
CS 5 5 1 1,,2 8 11 28 5 11 12 13 14 15 16 17 18 5,,1 1,,1 2,,1 3,,1 4,,1 5,,1 6,,1 7,,1 8 2 ion

.Inagreementwiththisclassificationoftheclassicalionicbonds,ELFshows thatthesebondsonlypossess

5 5

,CSbondingis

,andinELF,byadepletedbasinpopulationwithlargevarianceandcovariance .Inaddition,homonuclearCSbondingis .ItshouldbenotedthatthecharacterizationofCSbondingby

characterizedinAIMbyasmallnegativeorapositiveLaplacianoftheelectrondensity molecularorbitalbondingtheoryordensityfunctionals partitioning(KitauraMorokuma

29 29 5 11 5,,1 1

AIMandELFelectron-densityanalysesisindependentofthetheoreticalmethodthatisusedtocomputethewavefunctionorelectrondensity;forexample, ,showingthatthelattermethodseffectivelyaccountforCSbonding,evenifnotintheexplicitway
31 31

achievedbyVBtheory.ThereisofcoursearelationshipbetweentheVBmethodandmolecularorbitalordensity-functional-theory-basedmethodsofenergy ,ZieglerRauk
30 30

,BaerendsBickelhaupt

).Althoughthesemethodsdonot,asyet,makeprovisionstocharacterizeCS

bonding,theyshareafewessentialfeatureswiththeVBmodel:themajoroneisthePaulirepulsionthatistheoriginofthelargecovalentionicresonance energy.InthisrespecttheseenergypartitionmethodsshouldseeadifferencebetweenbondssuchasH andF (ref.3 2 ). 3

2 2

P h y s i c a l o r i g i n s o f C S b o n d i n g ThelargeRE
CS

quantityofCSbondsisanoutcomeofthemechanismnecessarytoestablishequilibriumandoptimumbondingduringbondformation.This
5 12 33 5,,1 2,,3 3

mechanismhasbeenanalysedbeforeindetail onefindsthatgenerallyr
ATOM

;herewepresentasimpleranalysis.Bycomparingtheatomicandcovalentradiiintheperiodictable,
3 4,,3 5,,3 6,,3 7,,3 8,,3 9,,4 0 34 35 36 37 38 39 40

<r

cov

.Thismeansthatasatoms(fragments)bindtheyshrink.Theshrinkagecausesasteepincreaseinthekineticenergyof .Thus,theshrinkagetipsthevirialratio

thefragments,whichexceedstheloweringofthepotentialenergyduetothediminishedsize energycanbereducedtorestorethevirialratio
1 2,,3 4 12 34

ofthekinetic(T)versuspotential(V)energiesoff-equilibrium(V/T=-2atequilibrium).Thecovalentionicresonanceisthemeanswherebythekinetic ,andthisistrueinallbonds.Thekineticenergyriseduetoshrinkageisproportionaltothe compactnessofbondingpartners,andtherefore,asthefragmentsinbondingbecomemoreelectronegative,andhencemorecompact,thekineticenergy riseduetoshrinkagewillgetsteeper.Moreover,whentheatoms(fragments)bearlone-pairs,athree-electronrepulsionappearsbetweenthe lone-pairof onefragmentandthebondingelectronoftheother.Thiseffectwilldestabilizethecovalentstructure,asenvisagedoriginallybySanderson

41 41

,whotermed

thisasthelone-pairbond-weakeningeffect(LPBWE);thisPaulirepulsionraisesthekineticenergyofthebond,andtheeffectbecomesmoresevereasthe numberoflonepairsontheatomincreases.Aselectronegativefragmentsarealsolone-pairrich,thecombinationofatomicshrinkageandLPBWEcausesa highexcesskineticenergy.Insuchcases,theresonanceenergythatwillberequiredtorestorethevirialratiobecomesnecessarilyverylarge,andonefinds bondswithweakenedcovalentstructuresandlargeRE bond. TheaboverelationshipsareillustratedinF i g . 3 ;partashowsaplotofthecovalentpartoftheLaplacianagainstD F lowerquadrant,whereD

cov cov CS

quantities.Thus,farfrombeingamerephenomenologicalmodel,CSbondingisafundamental

mechanismthatisnecessarytoadjustthekineticandpotentialenergytothevirialratioatequilibrium,inresponsetothePaulirepulsivestrainexertedonthe

forhomonuclearbonds

11 11

.Intheright

>0and

cov

<0,arethebondswithstabilizedcovalentbonding.Thesecondgroup,intheupperleftquadrant,involves
2

electronegativeandlone-pair-richatomsand'invertedcarbons',whichundergoCSbonding.Itcanbeseenthatthisbonding-typeisassociatedwith weakenedcovalentspinpairing(D
cov

<0),owingtolone-pairrepulsion,whichraisesthekineticenergy,asseenfromthepositivesignof

cov

F i g u r e 3 : C o r r e l a t i o n o f t h e c h a r g e - s h i f t / c o v a l e n t b o n d c h a r a c t e r w i t h t h e r e p u l s i v e / a t t r a c t i v e n a t u r eo f t h e c o v a l e n t i n t e r a c t i o n , a n d w i t h t h e e l e c t r o n e g a t i v i t i e s o f t h e b o n d e d a t o m s .

a ,ThecovalentLaplacian,

cov

,versusthecovalentbondenergy,D
A

cov

foraseriesofhomonuclearbonds.b ,RE b

CS

(AA)

versustheelectronegativityofA( RE
CS

).c ,RE c

CS

forAAandAXbondsversustheaverageelectronegativityofthebond.d , d

for -bondsversustheaverageelectronegativityofthebond.e ,AplotoftheresonanceLaplacianversustheaverage e

electronegativityofthebond.Partsa ande reproducedwithpermissionfromref.1 1 ,2009Wiley.Partsb d reproduced a e 1 b withpermissionfromref.5 ,2005Wiley. 5 F u l l s i z e i m a g e ( 3 9 K B ) F i g u r e 3 b showstheRE quantitiesforhomonuclearAAbonds,plottedagainsttheelectronegativity(

15 15

CS

)ofA.Itisseenthatineachperiod,RE
5 5

CS

increasesastheelectronegativtyincreases.F i g u r e 3 c showsasimilarplotbutnowusingbothhomonuclearandheteronuclearbonds ,andF i g . 3 d F F showsthesametrendfor -bonds .ItisapparentthattheRE

CS

quantityofthebondgenerallyincreasesastheaverageelectronegativityofthebond
11 11

partnersincreases.Finally,F i g . 3 e showsthattheresonancecomponentoftheLaplacianthatgaugestheloweringofthekineticenergybycovalentionic F mixingalsocorrelateswiththeaverageelectronegativityofthebond orbitaloverlap,andinfact,theRE

CS

.InthisrespectwenotethatwhatdeterminestheRE
5 12 5,,1 2 2

CS

quantityisnotthesimple
2

increasesastheoverlapbecomessmaller

.Forexample,theorbitaloverlapinH ismuchlargerthaninF ,
CS

whereasthecovalentionicresonanceenergybehavesintheoppositeway.ThisunderscorestherelationshipofRE inthebondingregionratherthantothesimple'sharingofdensity'asincovalency.

totheexchangerepulsiondecrease

TheexchangerepulsionpressurethatisassociatedwiththelonepairsofelectronegativefragmentsisnottheonlyfactorthatcanpromoteCSbonding.A recentlyidentifiedadditionalfactor
5 12 13 14 17 5,,1 2,,1 3,,1 4,,1 7

wasexpressedinbondsbetweenmetalloidsofgroup14andelectronegativegroups,forexampleallthe
3 17 17

SiF,SiClandGeClbondsinT a b l e 1 .TheVBcalculationsforthesebondsshowthatthecorrespondingioniccurvefortheMe SiClbond,forexample, T ismuchdeeperthanthatforthecorrespondingMe CClbond

3 3 + 3 +

.Moreover,theioniccurveMe Si Cl hasatighterminimumthanMe C Cl .Thismeans

3 3

thattheMe Si ionissmallerthantheMe C ionalongthelineofapproachtothecentralatom(siliconorcarbon),inharmonywiththefactthatthechargeis completelylocalizedonSiinMe Si ,whereasitishighlydelocalizedinMe C .Thiscausestheionicandcovalentstructurestobecloseinenergyin

3 3 + +

Me SiCl,thusleadingtoahighRE
3

CS

quantity,whichisapparentfromT a b l e 1 fortheSiClbond T

17 17

M a n i f e s t a t i o n s o f C S b o n d i n g HavingshowntheemergenceofCSbondinganditspromotingfactors,herewefollowwithsomeevidenceforthesignatureofthisbondtypeinthechemical behaviour. E v i d e n c e o f C S b o n d i n g f r o m e l e c t r o n - d e n s i t y m e a s u re m e n t s .TheexistenceoftheCSbondfamilywilleventuallybeconsolidatedby experimentaldeterminationoftheLaplacianofvariousbonds,asalreadydonefor[1.1.1]propellanederivatives

25 25

,N O (ref.4 2 )andothers 4
2 4

21 21

.Inthe

meantime,theexistenceoftwodistinctfamiliesalreadyemergesfromelectron-density-differencemaps(measurableexperimentally),whichplotthe differencebetweentheactualmoleculardensityandthedensityofareferencestatemadefromsphericalatoms( themolecule.Thesedata 'no-densitybonds'with referenceatomicstate

47 47 4 3,,4 4,,4 5,,4 6 43 44 45 46

Mol

Ref

),atthesamegeometryas
25 25

clearlyshowabond-groupwith

>0,whichcoincideswiththeclassicalcovalentbond,andasecondgroupof ;theCCbondsin <0.Althoughthedeformationdensitydependsonthedefinitionofthe

<0,whichcoincideswiththeCSbondingfamily.Theexampleof[1.1.1]propellaneshowsthetwobondtypes >0,whereasthe'inverted'(CC)has
4 3,,4 4,,4 5 43 44 45

thewingsarenormalcovalentbondswith

,theexampleofpropellanes

,wherethesamemoleculedisplaystwoCCbonds,onehavingnegativeandtheother

positivedeformationdensities,isfreeofthislimitation. E v i d e n c e f o r C S b o n d i n g i n c h e m i c a l r e a c t i v i t y.Thefindingsthathalogen-transferreactions(andespeciallyoffluorine)havemuchlargerbarriers (by>20kcalmol forX=F)thanthecorrespondinghydrogen-transferprocesses,isassociatedwiththeRE recently

16 16 -1 CS

quantityofthebond

16 16

.Asweshowed

,thebarrierdifferencebetweenthetwoseriesfollowsaverysimplerelationship:

NotethatmeasurementofthebarrierdifferenceforthetwoseriesenablesquantificationoftheCSresonanceenergyfromexperimentalbarriers. R a r i t y o f s i l i c e n i u m i o n s i n c o n d e n s e d p h a s e s.AsSiXbondshavelargeRE
17 17 + CS

values,theirchemicalbehaviourcanbecontrastedwithcarbon,
8 8

whichdoesnotgenerallyinvolveCSbonds.Oneofthemanifestationsistherareionicchemistryofsiliconincondensedphases ,comparedwiththe ubiquityincarbon.ArecentVBstudyshowed thattheMe Si Cl structureinaqueoussolutionretainsthetightion-pairminimum,andthusmixesstrongly

3 CS

withthecovalentstructureandacquireslargeRE

.ThislargeRE
3

CS

isthemajorreasonwhythebondwillnotundergoheterolysisinsolution(butwillprefer
10 10

associativeprocesses),andwhyinthesolidstateevenPh SiOClO isacovalentsolid

3

bycontrasttothecarbonanalogue,whichhasanNa Cl -type

latticewithPh C andClO ions

3

48 48

andothers

49 49

C h a r t i n g t h e t e r r i t o r y o f C S b o n d i n g CSbondingoriginatesfromtheequilibriumconditionofthebond,definedbythevirialratio.Itispromotedbytwomainfactors. First,byexchangerepulsionthatweakensthecovalencyofthebondandinduceslargeRE manyothersmall-ringpropellanes. Second,fragmentsthatformextremelysmallcations,whichresembleaproton,withallthepositivechargelocatedatthecentralatom,likeinthesilicenium cation,R Si ,willpromoteCSbondingespeciallywithelectronegativeandlone-pair-richatoms

3 + 5 14 17 5,,1 4,,1 7 CS

values.Thisexcessiveexchangerepulsionistypicalto
18 18

electronegativeandlone-pair-richatoms,orbondsweakenedbyexchangerepulsionpressure,asthebridgeheadCCbondin[1.1.1]propellane

,and

Withthesepromoters,CSbondingformsadistinctgroupofbondingthattranscendsconsiderationofstaticchargedistribution,andthatpossessesunique chemicalsignatures.SomeofthesebondsarecollectedinT a b l e 1 .Butthereareothers,forexample, -bonds,indoublyandtriplybondedmolecules T

50 50 1 5,, 15

,andinmanyhypercoordinatedcompounds(forexample,PCl ,XeF andsoon) .ClearlymanymoreCSbondsarewaitingtobeidentifiedinnew

5

5 5

molecules. Futuredirectionsaremany.Afruitfuloneishypercoordinationandaggregation.Thus,forexample,thesmallsizeofR Si ,andheavieranalogues,mean

3 +

thattheywilltendtoformhypercoordinatedcompounds;insolution,inthesolidstate beenreported
55 55 5 2,,5 3 52 53 +

51 51

andeveninthegasphase,wheresomeunusualmoleculeshave
54 54

,andbridged(Si---X---Si) systems,whichparticipateincatalyticbondexchangereactions
2 4

.Metalmetalbondsinsomebimetallic
2

complexescouldwellbeCSbonds,asinM (formamidinate) complexes(M=Nb,Mo,Tc,Ru,Rh,Pd)wherelargepositivevaluesof reported

2

(r )havebeen
c

.Otherdirectionsinvolvethegenerationof[1.1.1]propellaneinwhichtheCH wingsaresubstitutedbyheteroatomsthatexertexchangerepulsion
+ 56 56

pressureontheinvertedCCbond,forexample,HN,OandS(ref.1 8 ).Thein-plane -typebondinortho-benzyneisanotherbondthatisaffectedby 1 exchangerepulsionpressure.Protonationormethylation(byMe )ofCNbondsmayconvertthemintoCSbonds andmayhavemechanisticeffects,asintheprotonatedarginineinthemechanismofnitricoxidesynthase pressure

58 58 57 57

,afactthatmayconcernDNAbases,

.Mostbondsunderimmenseexternal

arelikelytobeCSbonds,andencapsulatedhighlypositiveionswillbeCS-bound

5 9,,6 0 59 60

Thus,CSbondingisnotmerelyanacademicabstraction.AsnewexamplesorexperimentalmanifestationsofCSbondingwillstarttoaccumulateandbe recognized,theconceptofCSbondingwillgraduallybeacceptedbythechemicalcommunity,andwillfindmoreapplications.

References
1. Lewis,G.N.Theatomandthemolecule.J.Am.Chem.Soc.3 8 ,762785(1916).|A r t i c l e |C h e m P o r t | 3 A C 2. Heitler,W.&London,F.Wechselwirkungneutraleratomeunhomopolarebindungnachderquantenmechanik.Zeits.frPhysik.4 4 ,455472 4 (1927).|A r t i c l e |C h e m P o r t | A C 3. Pauling,L.TheNatureoftheChemicalBond(CornellUniv.Press,1939). 4. London,F.Zurquantentheoriederhomopolarenvalenzzahlen.Zeits.frPhysikA4 6 ,455477(1928).|A r t i c l e |C h e m P o r t | 4 A C 5. Shaik,S.,Danovich,D.,Silvi,B.,Lauvergnat,D.&Hiberty,P.C.Charge-shiftbondingaclassofelectron-pairbondsthatemergesfromvalence bondtheoryandissupportedbytheelectronlocalizationfunctionapproach.Chem.Eur.J.1 1 ,63586371(2005).|A r t i c l e |C h e m P o r t | 1 A C 6. Bader,R.F.W.&Nguyen-Dang,T.T.QuantumtheoryofatomsinmoleculesDaltonrevisited.Adv.Quant.Chem.1 4 ,63124(1981).|C h e m P o r t | 1 C 7. Henn,J.,Ilge,D.,Leusser,D.,Stalke,D.&Engles,D.Ontheaccuracyoftheoreticallyandexperimentallydeterminedelectrondensitiesofpolar bonds.J.Phys.Chem.A1 0 8 ,94429452(2004).|A r t i c l e |C h e m P o r t | 1 A C 8. Apeloig,Y.inTheChemistryofOrganicSiliconCompoundsVol.1(edsApeloig,Y.&Rappoport,Z.)Ch.2(Wiley,1989). 9. Apeloig,Y.&Stanger,A.Thefirstdemonstrationofsolvolyticgenerationofasimplesiliceniumion(R Si ).Accessvia1,2-methylmigration.J.Am.
3 +

Chem.Soc.1 0 9 ,272273(1987).|A r t i c l e |C h e m P o r t | 1 A C
10. Prakash,G.K.S.etal.Triphenylsilylperchloraterevisited: Siand ClNMRspectroscopyandX-raycrystallographyshowingcovalentnaturein bothsolutionandthesolidstate.Difficultiesinobservinglong-livedsilylcationsinthecondensedstate.J.Am.Chem.Soc.1 0 9 ,51235126 1 (1987).|A r t i c l e |C h e m P o r t | A C
29 35

11. Zhang,L.,Ying,F.,Wu,W.,Hiberty,P.C.&Shaik,S.Topologyofelectronchargedensityforchemicalbondsfromvalencebondtheory:aprobeof bondingtypes.Chem.Eur.J.1 5 ,29792989(2009).|A r t i c l e |C h e m P o r t | 1 A C 12. Shaik,S.,Maitre,P.,Sini,G.&Hiberty,P.C.Thecharge-shiftbondingconcept.Electron-pairbondswithverylargeionic-covalentresonance energies.J.Am.Chem.Soc.1 1 4 ,78617866(1992).|A r t i c l e |C h e m P o r t | 1 A C 13. Lauvergnat,D.,Hiberty,P.C.,Danovich,D.&Shaik,S.ComparisonofC-ClandSi-Clbonds.Avalencebondstudy.J.Phys.Chem.1 0 0 ,57155720 1 (1996).|A r t i c l e |C h e m P o r t | A C 14. Shurki,A.,Hiberty,P.C.&Shaik,S.Charge-shiftbondingingroupIVBhalides:avalencebondstudyofMH -Cl(M=C,Si,Ge,Sn,Pb)molecules.J.
3

Am.Chem.Soc.1 2 1 ,822834(1999).|A r t i c l e |C h e m P o r t | 1 A C
15. Galbraith,J.M.,Blank,E.,Shaik,S.&Hiberty,P.C. -bondinginsecondandthirdrowmolecules:testingthestrengthofLinus'sblanket.Chem.Eur.

J.6 ,24252434(2000).|A r t i c l e |C h e m P o r t | 6 A C
16. Hiberty,P.C.,Megret,C.,Song,L.,Wu,W.&Shaik,S.Barriersofhydrogenabstractionvshalogenexchange:anexperimentalmanifestationof charge-shiftbonding.J.Am.Chem.Soc.1 2 8 ,28362843(2006).|A r t i c l e |P u b M e d |C h e m P o r t | 1 A P C 17. Su,P.,Song,L.,Wu,W.,Shaik,S.&Hiberty,P.C.Heterolyticbonddissociationinwater:whyisitsoeasyforC H ClbutnotforC H SiCl?J.Phys.
4 9 3 9

Chem.A1 1 2 ,29882997(2008).|A r t i c l e |P u b M e d |C h e m P o r t | 1 A P C
18. Wu,W.,Gu,J.,Song,J.,Shaik,S.&Hiberty,P.C.Theinvertedbondin[1.1.1]propellaneisacharge-shiftbond.Angew.Chem.Int.Ed.4 8 , 4 14071410(2009).|A r t i c l e |C h e m P o r t | A C 19. Bader,R.F.W.AtomsinMolecules:AQuantumTheory(OxfordUniv.Press,1990). 20. Silvi,B.&Savin,A.Classificationofchemicalbondsbasedontopologicalanalysisofelectronlocalizationfunctions.Nature3 7 1 ,683686 3 (1994).|A r t i c l e |C h e m P o r t | A C 21. Coppens,P.Chargedensitiescomeofage.Angew.Chem.Int.Ed.4 4 ,68106811(2005).|A r t i c l e |C h e m P o r t | 4 A C 22. Coppens,P.X-rayDensitiesandChemicalBonding(OxfordUniv.Press,1997). 23. Kraka,E.&Cremer,D.inTheoreticalModelsofChemicalBondingPart2(ed.Maksi ,Z.B.)457543(Springer,1990). 24. Silvi,B.Thespin-paircompositionsaslocalindicatorsofthenatureofthebonding.J.Phys.Chem.A1 0 7 ,30813085 1 (2003).|A r t i c l e |C h e m P o r t | A C 25. Messershmidt,M.etal.Electrondensityandbondingatinvertedcarbonatoms:anexperimentalstudyofa[1.1.1]propellanederivative.Angew.

Chem.Int.Ed.4 4 ,39253928(2005).|A r t i c l e |C h e m P o r t | 4 A C
26. Polo,V.,Andres,J.&Silvi,B.Newinsightonthebridgecarbon-carbonbondinpropellanes:atheoreticalstudybasedontheanalysisoftheelectron localizationfunction.J.Comput.Chem.2 8 ,857864(2007).|A r t i c l e |P u b M e d |C h e m P o r t | 2 A P C 27. Lusar,R.,Beltrn,A.,Andrs,J.,Noury,S.&Silvi,B.Topologicalanalysisofelectrondensityindepletedhomopolarchemicalbonds.J.Comput.

Chem.2 0 ,15171526(1999).|A r t i c l e 2 A
28. Rincon,L.&Almeida,R.Onthetopologyoftheelectronchargedensityatthebondcriticalpointoftheelectron-pairbond.J.Phys.Chem.A1 0 2 , 1 92449254(1998).|A r t i c l e |C h e m P o r t | A C 29. Kitaura,K.&Morokuma,K.AnewenergydecompositionschemeformolecularinteractionswithintheHartree-Fockapproximation.Int.J.Quantum

Chem.1 0 ,325340(1976).|A r t i c l e |C h e m P o r t | 1 A C
30. Ziegler,T.&Rauk,A.OnthecalculationofbondingenergiesbytheHartree-Fock-Slatermethod.Theor.Chim.Acta4 6 ,110(1977).|C h e m P o r t | 4 C 31. Velde,G.T.etal.ChemistrywithADF.J.Comput.Chem.2 2 ,931967(2001).|A r t i c l e 2 A 32. Krapp,A.,Bickelhaupt,F.M.&Frenking,G.Orbitaloverlapandchemicalbonding.Chem.Eur.J.1 2 ,91969216(2006).|A r t i c l e |C h e m P o r t | 1 A C 33. Hiberty,P.C.,Ramozzi,R.,Song,L.,Wu,W.&Shaik.S.Thephysicaloriginoflargecovalent-ionicresonanceenergiesinsometwo-electronbonds.

FaradayDiscuss.1 3 5 ,261272(2006).|A r t i c l e |C h e m P o r t | 1 A C
34. Kutzelnigg,W.inTheoreticalModelsofChemicalBondingPart2(ed.Maksi ,Z.B.)144(Springer,1990). 35. Ruedenberg,K.Thephysicalnatureofthechemicalbond.Rev.Mod.Phys.3 4 ,326376(1962).|A r t i c l e |C h e m P o r t | 3 A C 36. Feinberg,M.J.&Ruedenberg,K.Paradoxicalroleofthekinetic-energyoperatorintheformationofthecovalentbond.J.Chem.Phys.5 4 , 5 14951591(1971).|A r t i c l e |C h e m P o r t | A C 37. Wilson,C.Q.&Goddard,W.A.III.Theroleofkineticenergyinchemicalbinding.Theor.Chim.Acta.2 6 ,195210(1972).|A r t i c l e |C h e m P o r t | 2 A C 38. Rozendaal,A.&Baerends,E.J.Amomentum-spaceviewofthechemicalbond.IThefirst-rowhomonucleardiatomics.Chem.Phys.9 5 ,5791 9

(1985).|A r t i c l e |C h e m P o r t | A C 39. Ruedenberg,K.&Schmidt,M.Whydoeselectronsharingleadtocovalentbonding?Avariationalanalysis.J.Comput.Chem.2 8 ,391410 2 (2007).|A r t i c l e |P u b M e d |C h e m P o r t | A P C 40. Bickelhaupt,F.M.&Baerends,E.J.Kohn-Shamdensityfunctionaltheory:predictingandunderstandingchemistry.Rev.Comput.Chem.1 5 ,186 1 (2000).|C h e m P o r t | C 41. Sanderson,R.T.PolarCovalence(AcademicPress,1983). 42. Messerschmidt,M.,Wagner,A.,Wong,M.W.&Luger,P.AtomicpropertiesofN O basedonitsexperimentalchargedensity.J.Am.Chem.Soc.
2 4

1 2 4 ,732733(2002).|A r t i c l e |P u b M e d |C h e m P o r t | A P C 43. Dunitz,J.D.&Seiler,P.TheabsenceofbondingelectrondensityincertaincovalentbondsasrevealedbyX-rayanalysis.J.Am.Chem.Soc.1 0 5 , 1 70567058(1983).|A r t i c l e |IIS I |C h e m P o r t | A C 44. Dunitz,J.D.,Schweizer,W.B.&Seiler,P.X-raystudyofthedeformationdensityintetrafluoroterephthalodinitrile:weakbondingdensityintheC-F bond.Helv.Chem.Acta6 6 ,123133(1983).|A r t i c l e |C h e m P o r t | 6 A C 45. Coppens,P.,Yang,Y.W.,Blessing,R.H.,Cooper,W.F.&Larsen,F.K.Theexperimentalchargedistributioninsulfurcontainingmolecules.Analysis ofcyclicoctasulfurat300and100K.J.Am.Chem.Soc.9 9 ,760766(1977).|A r t i c l e |C h e m P o r t | 9 A C 46. Savariault,J.-M.&Lehmann,M.S.ExperimentaldeterminationofthedeformationelectrondensityinhydrogenperoxidebycombinationofX-rayand neutrondiffractionmeasurements.J.Am.Chem.Soc.1 0 2 ,12981303(1980).|A r t i c l e |IIS I |C h e m P o r t | 1 A C 47. Ruedenberg,K.&Schwarz,W.H.E.Nonsphericalatomicgroundstatedensitiesandchemicaldeformationdensitiesfromx-rayscattering.J.Chem.

Phys.9 2 ,49564969(1990).|A r t i c l e |C h e m P o r t | 9 A C
48. GomesdeMesquita,A.H.,MacGillavryC.H.&Eriks,K.Thestructureoftriphenylmethylperchlorateat85C.ActaCrystallogr.1 8 ,437443 1 (1965).|A r t i c l e |C h e m P o r t | A C 49. Kim,K.-C.etal.Crystallographicevidenceforafreesilyliumion.Science2 9 7 ,825827(2002).|A r t i c l e |P u b M e d |C h e m P o r t | 2 A P C 50. Ploshnik,E.TheTripleBondAValenceBondTheoryPointOfViewMScThesis,HebrewUniv.(2005). 51. Kost,D.&Kalikhman,I.Hypercoordinatesiliconcomplexesbasedonhydrazineligands.Aremarkablyflexiblemolecularsystem.Acc.Chem.Res. 4 2 ,303314(2009).|A r t i c l e |P u b M e d |C h e m P o r t | A P C 52. Dvalos,J.Z.,Herrero,R.,Abboud,J.-L.M.,M,O.&Yez,M.Howcancarbonbecovalentlyboundtofiveligands?ThecaseofSi (CH ) .Angew.
2 3 7

Chem.Int.Ed.4 6 ,381385(2007).|A r t i c l e |C h e m P o r t | 4 A C
53. Fernndez,I.,Uggerud,E.&Frenking,G.Stablepentacoordinatecarbocations:structureandbonding.Chem.Eur.J.1 3 ,86208626 1 (2007).|A r t i c l e |C h e m P o r t | A C 54. Panisch,R.,Bolte,M.&Mller,T.Hydrogenandfluorine-bridgeddisilylcationsandtheiruseincatalyticC-Factivation.J.Am.Chem.Soc.1 2 8 , 1 96769682(2006).|A r t i c l e |P u b M e d |C h e m P o r t | A P C 55. Llusar,R.,Beltran,A.,Andrs,J.,Fuster,F.&Silvi,B.Topologicalanalysisofmultiplemetal-metalbondsindimersoftheM (formamidinate) type
2 4

withN=Nb,Mo,Tc,Ru,Rh,andPd.J.Phys.Chem.A1 0 5 ,94609466(2001).|A r t i c l e |C h e m P o r t | 1 A C 56. Shaik,S.inMoleculesinNaturalScienceandMedicine:AnEncomiumforLinusPauling(edsMaksi ,Z.B.&Eckert-Maksi ,M.)253266(Ellis Horwood,1991). 57. Cho,K.B.,Carvajal,M.A.&Shaik,S.Firsthalf-reactionmechanismsofnitricoxide.Theroleofprotonandoxygencoupledelectrontransfersinthe reactionbyquantummechanical/molecularmechanicalcalculations.J.Phys.Chem.B1 1 3 ,336346(2009).|A r t i c l e |P u b M e d |C h e m P o r t | 1 A P C 58. Grochala,W.,Hoffmann,R.,Feng,J.&Ashcroft,N.W.Thechemicalimaginationatworkinverytightplaces.Angew.Chem.Int.Ed.4 6 ,36203642 4 (2007).|A r t i c l e |C h e m P o r t | A C 59. Dognon,J.-P.,ClavaguraC.&Pyykk,P.Apredictedorganometallicseriesfollowinga32-electronprinciple:An@C (An=Th,Pa ,U ,Pu ).J.
28 + 2+ 4+

Am.Chem.Soc.1 3 1 ,238243(2009).|A r t i c l e |P u b M e d |C h e m P o r t | 1 A P C
60. Rupar,P.,Staroverov,V.N.&Baines,K.M.Acryptand-encapsulatedgermanium(II)dication.Science3 2 2 ,13601363 3 (2008).|A r t i c l e |P u b M e d |C h e m P o r t | A P C 1. InstituteofChemistryandTheLiseMeitner-MinervaCenterforComputationalQuantumChemistry,TheHebrewUniversityofJerusalem,91904, Jerusalem,Israel. 2. StateKeyLaboratoryofPhysicalChemistryofSolidSurfacesandCollegeofChemistryandChemicalEngineering,XiamenUniversity,Xiamen 361005,P.R.China.

3. LaboratoiredeChimiePhysique,GroupedeChimieThorique,CNRSUMR8000,UniversitdeParis-Sud,91405OrsayCdex,France. Correspondenceto:SasonShaik e-mail:s a s o n @ y f a a t . c h . h u j i . a c . i l s Correspondenceto:WeiWu e-mail:w e i w u @ x m u . e d u . c n w Correspondenceto:PhilippeC.Hiberty e-mail:p h i l i p p e . h i b e r t y @ l c p . u - p s u d . f r p

ISSN 1755-4330 About NPG Contact NPG RSS web feeds Help EISSN 1755-4349 Privacy policy Legal notice Accessibility statement Nature News Naturejobs Nature Asia Nature Education
2009 Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved. partner of AGORA, HINARI, OARE, INASP, CrossRef and COUNTER
3 3 2 2 1 1

Search:

go