Table Of ContentStructure and Bonding 170
Series Editor:
D.M.P. Mingos
Editor
D. Michael P. Mingos
The Chemical
Bond II
100 Years Old and Getting Stronger
170
Structure and Bonding
SeriesEditor:
D.M.P.Mingos,Oxford,UnitedKingdom
EditorialBoard:
F.A.Armstrong,Oxford,UnitedKingdom
X.Duan,Beijing,China
L.H.Gade,Heidelberg,Germany
K.R.Poeppelmeier,Evanston,IL,USA
G.Parkin,NewYork,USA
M.Takano,Kyoto,Japan
Aims and Scope
The series Structure and Bonding publishes critical reviews on topics of research
concerned withchemical structure andbonding.Thescope ofthe series spans the
entirePeriodicTableandaddressesstructureandbondingissuesassociatedwithall
of the elements. It also focuses attention on new and developing areas of modern
structuraland theoretical chemistrysuch asnanostructures, molecularelectronics,
designed molecular solids, surfaces, metal clusters and supramolecular structures.
Physical and spectroscopic techniques used to determine, examine and model
structures fall within the purview of Structure and Bonding to the extent that the
focus is on the scientific results obtained and not on specialist information
concerning the techniques themselves. Issues associatedwith the development of
bonding models and generalizations that illuminate the reactivity pathways and
ratesofchemicalprocessesarealsorelevant.
The individual volumes in the series are thematic. The goal of each volume is to
givethereader,whetheratauniversityorinindustry,acomprehensiveoverviewof
an area where new insights are emerging that are of interest to a larger scientific
audience.Thuseachreviewwithinthevolumecriticallysurveysoneaspectofthat
topicandplacesitwithinthecontextofthevolumeasawhole.Themostsignificant
developmentsofthelast5to10yearsshouldbepresentedusingselectedexamples
to illustrate the principles discussed. A description of the physical basis of the
experimentaltechniquesthathavebeenusedtoprovidetheprimarydatamayalso
beappropriate,ifithasnotbeencoveredindetailelsewhere.Thecoverageneednot
be exhaustive in data, but should rather be conceptual, concentrating on the new
principlesbeingdevelopedthatwillallowthereader,whoisnotaspecialistinthe
area covered, to understand the data presented. Discussion of possible future
researchdirectionsintheareaiswelcomed.
Reviewarticlesfortheindividualvolumesareinvitedbythevolumeeditors.
In references Structure and Bonding is abbreviated Struct Bond and is cited as a
journal.
Moreinformationaboutthisseriesathttp://www.springer.com/series/430
D. Michael P. Mingos
Editor
The Chemical Bond II
100 Years Old and Getting Stronger
With contributions by
(cid:2) (cid:2) (cid:2) (cid:2)
S. Alvarez B. Braida D. Danovich A. Falceto
(cid:2) (cid:2) (cid:2) (cid:2)
A. Haaland P.C. Hiberty M. Kohout P.L.A. Popelier
(cid:2) (cid:2) (cid:2)
S. Shaik B. Silvi M. Tilset W. Wu
Editor
D.MichaelP.Mingos
UniversityofOxford
Oxford,UnitedKingdom
ISSN0081-5993 ISSN1616-8550 (electronic)
StructureandBonding
ISBN978-3-319-33520-9 ISBN978-3-319-33522-3 (eBook)
DOI10.1007/978-3-319-33522-3
LibraryofCongressControlNumber:2016940193
©SpringerInternationalPublishingSwitzerland2016
Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartof
the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
or information storage and retrieval, electronic adaptation, computer software, or by similar or
dissimilarmethodologynowknownorhereafterdeveloped.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexempt
fromtherelevantprotectivelawsandregulationsandthereforefreeforgeneraluse.
Thepublisher,theauthorsandtheeditorsaresafetoassumethattheadviceandinformationinthis
book are believed to be true and accurate at the date of publication. Neither the publisher nor the
authors or the editors give a warranty, express or implied, with respect to the material contained
hereinorforanyerrorsoromissionsthatmayhavebeenmade.
Printedonacid-freepaper
ThisSpringerimprintispublishedbySpringerNature
TheregisteredcompanyisSpringerInternationalPublishingAGSwitzerland
Preface
These three volumes ofStructure and Bonding celebrate the 100th anniversary of
theseminalpapersbyLewisandKossel.Thesepapers,whichformedthebasisof
thecurrentviewofthechemicalbond,werepublishedindependentlyin1916and
have greatly influenced the development of theoretical chemistry during the last
century. Their essential ideas, which were initially formulated within classical
Newtonian framework, have withstood many experimental tests and proved to be
sufficiently flexible to incorporate the newer quantum mechanical ideas, which
emerged in the 1920s and 1930s. Most importantly, Lewis’ description of the
covalent bond provided a graphical notation and a language for experimental
chemists, which enabled generations of chemists to constructively discuss and
predictthestructuresofmoleculesandgraphicallyrepresentthecourseofchemical
reactions.TheLewisandKosseldescriptionsofchemicalbondingarecornerstones
ofthe undergraduate curriculum.Theyhave achieved thispre-eminent distinction
by evolving and incorporating a flexible view of chemical bonding, based on the
symmetry characteristics and radial distribution functions of atomic orbitals. The
development of a universally accepted notation for representing the bonds in
inorganic and organic molecules has been particularly significant. Spectroscopic
andstructuralresults,whichemergedaschemistryincorporatedquantummechan-
icalconcepts,provideddetailedinformationconcerningthestructuresofmolecules
notonlyinthesolidstatebutalsointheliquidandgasphases.Thesehaveprovided
increasingly rigorous tests of the bonding models, which emerged from the quan-
tummechanicaldescriptionofthechemicalbond.
Theideatocelebratethisimportant anniversary inchemicalevolution struck a
chord with leading figures in the area of theoretical chemistry and resulted in the
submission of 18 chapters, and it became necessary to produce three separate
volumes of Structure and Bonding to satisfactorily account for the enormous
influence Lewis and Kossel’s seminal ideas had on modern chemistry. Following
a historical introduction by myself, Volume 1 contains chapters by Dietar Stalke,
Zhenyang Lin, Gernot Frenking, Jean-Francois Halet, Jen-Yves Saillard, Jose´
M. Goicoechea, John McGrady and Michael Hall covering a variety of
v
vi Preface
experimentalandtheoreticalstudiesoftopicalchemicalbondingissues.Examples
includetheimplicationsofexperimentallydeterminedelectrondensitiesonLewis
bondstructures,theLewisdescriptionoflonepairsintransitionmetalcomplexes,
dative Lewis bonds, the bonding patterns in large metal clusters and the role of
carbonyl ligands in stabilising such clusters and the electronic properties of
endohedralmetalclusters.
Volume2startswithadetailedaccountofLewisandKossel’slegacyindefining
thebondinginionicandcovalentcompoundsofmaingroupelementsandaddresses
thethermochemicalandbondlengthimplicationsoftheLewisandKosselmodels.
The subsequent chapters by Paul Poppelier, Miroslav Kohout, Sason Shaik,
Philippe Hiberty and Bernard Silvi use highly accurate theoretical calculations to
address and explore the fundamental nature of the covalent bond. Discussions of
quantum chemical topology, the definition of electron pairs in positional space,
provideadeeperinsightintothenatureofthechemicalbondandtherelevanceof
the ELF topological approach to the Lewis bond model and the evolution of
electronpairbondingincovalent,ionicandchargeshiftbonds.TheLewisdescrip-
tion of the chemical bond was limited to single, double and triple bonds, but in
recent years compounds with bond orders greater than three have become com-
monplace, and the final chapter by Santiago Alvarez compares the electronic
characteristicsofCr–Crquadrupleandquintuplebonds.
InVolume3,theimplicationsoftheLewisbondingideasformoderninorganic,
organic and organometallic chemistry are discussed by Douglas Stephen, Philip
Miller, Robert Crabtree, Malcolm Green, Ged Parkin, Didier Bourissou and
Ghenwa Bouhadir. These fascinating articles demonstrate how non-conventional
Lewisacidsandbaseshavebeenusedtodevelopnewchemistrybasedonfrustrated
Lewis pairs and describe the modern coordination chemistry of triphosphine
ligands and its catalytic implications. Lewis developed the concept that bases
function by donating non-bonding electron pairs, but Crabtree recounts how this
view has had to be modified by the discovery of complexes where π-bonds and
σ-bonds act as donors. Green and Parkin extend the basic Lewis concepts to
organometallic complexes with three-centre two-electron bonds. Bourissou and
Bouhadir describe compounds where the lone pairs on transition metals are able
tofunctionasLewisbases–afieldwhichhasgrownenormouslyinrecentyears.
Thisbriefsummaryprovidesanindicationofhowthebasicideasintroducedby
Lewis andKosselhaveblossomedoverthelast centuryasaresultofthenourish-
mentprovidedbyquantumtheoryandtheloveandattentionbestowedonthemby
successivegenerationsofchemists.Wehopethatthequalityanddepthofthemany
contributions in these three volumes will convince the reader that the sentiment
expressedinthetitleofthisseries“TheChemicalBond100YearsOldandGetting
Stronger”isappropriate.
Oxford,UK D.MichaelP.Mingos
April2016
Contents
LewisandKossel’sLegacy:StructureandBondinginMain-Group
Compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
ArneHaalandandMatsTilset
QuantumChemicalTopology. .. . . . . . . .. . . . . . .. . . . . . .. . . . . . . .. 71
PaulL.A.Popelier
ElectronPairsinPositionSpace. . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . 119
M.Kohout
NewLandscapeofElectron-PairBonding:Covalent,Ionic,
andCharge-ShiftBonds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
SasonShaik,DavidDanovich,BenoitBraida,WeiWu,
andPhilippeC.Hiberty
TheRelevanceoftheELFTopologicalApproachtotheLewis,Kossel,
andLangmuirBondModel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
BernardSilvi
ComparisonoftheCr–CrQuadrupleandQuintupleBonding
Mechanisms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
Andre´sFalcetoandSantiagoAlvarez
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
vii
StructBond(2016)170:1–70
DOI:10.1007/430_2015_192
#SpringerInternationalPublishingSwitzerland2016
Publishedonline:14February2016
’
Lewis and Kossel s Legacy: Structure
and Bonding in Main-Group Compounds
ArneHaalandandMatsTilset
Abstract In this article the authors provide a brief review of the main develop-
ments in our understanding of chemical bonding in representative compounds of
themaingroupelementsfromLewis’andKossel’sshell-settingarticlesin1916and
untilthepresent.
Keywords Bondenergies(cid:2)Coordinationcompounds (cid:2)Coordinationgeometries (cid:2)
Covalent bonds (cid:2) Covalent radii (cid:2) Dative bonds (cid:2) Electronegativity (cid:2) Hypervalent
compounds(cid:2)Ionicbonds(cid:2)Ionicradii(cid:2)Subvalentcompounds(cid:2)TheVSEPRmodel
Contents
1 Introduction:TheContributionsofG.N.Lewis,W.Kossel,andI.Langmuirfrom1916
to1923...................................................................................... 2
2 StructureandBondinginCrystallineAlkaliMetalHalides.............................. 6
2.1 StructureandBondinginGaseous,MonomericAlkaliMetalHalides............. 9
3 TheDihalidesoftheGroup2andGroup12Metals:FromIonictoPolarCovalent
Bonding..................................................................................... 11
3.1 StructuresandBondingintheSolidState........................................... 11
3.2 TheElectricalConductivitiesofMoltenDichlorides............................... 12
3.3 StructureandBondingintheGaseousMonomers.................................. 13
4 IonicRadii.................................................................................. 16
4.1 AtomicRadiifromUnitCellDimensions........................................... 16
4.2 TopologicalAnalysesofChargeDensitiesinIonicCrystalsand“CrystalRadii”. 19
5 ElectronegativityandElectronegativityCoefficients...................................... 20
6 CovalentCompounds:BondDistancesandCoordinationGeometries.................. 26
6.1 TheCrystalStructuresoftheGroup14Elements................................... 26
6.2 StandardTetrahedralBondRadii.................................................... 26
6.3 CovalentRadii........................................................................ 27
A.Haaland(*)andM.Tilset
DepartmentofChemistry,UniversityofOslo,POBox1033Blindern,0315Oslo,Norway
e-mail:[email protected];[email protected]
2 A.HaalandandM.Tilset
6.4 CoordinationGeometriesandspHybridAtomicOrbitals.......................... 29
6.5 CoordinationGeometriesandElectronCounts...................................... 31
6.6 InductiveEffectsonBondDistancesandBondEnergies........................... 34
7 CoordinationCompoundsandElectronDonor–AcceptorBonds......................... 37
7.1 Werner’sModelfortheStructuresofComplexSaltsofTransitionMetals........ 37
7.2 CoordinateLinksandElectronDonor–AcceptorBonds............................ 39
7.3 TheDifferenceBetweenCoordinateandNormalCovalentBonds:AmineBorane
andEthane............................................................................ 40
7.4 AminoboraneandDativeπ-Bonding................................................ 42
7.5 CoordinationCompoundsofAluminum............................................. 43
7.6 AluminumAmides,AluminumImides,andAluminumNitride:Al–NBonds
withPartialDativeCharacter........................................................ 45
7.7 SomeCoordinationCompoundsofZincandSilicon............................... 47
7.8 AnionicComplexes................................................................... 48
8 Lewis-ValentandSubvalentChloridesoftheGroup13and14Elements............... 50
8.1 TheInertElectronPair............................................................... 50
8.2 ThePolarCovalentChloridesoftheGroup12Metals............................. 50
8.3 TheGroup13ElementChlorides.................................................... 51
8.4 TheGroup14ElementChlorides.................................................... 54
9 CompoundsofHypervalentMain-GroupElements...................................... 55
9.1 TheStructuresofHypervalentCompoundsofPhosphorus......................... 56
9.2 TheStructuresofHypervalentCompoundsofSulfur............................... 58
9.3 HypervalentCompoundsofGroup17Elements.................................... 61
9.4 HypervalentCompoundsofXenon.................................................. 62
9.5 NitrogenOxidesandRelatedCompounds........................................... 62
9.6 d-OrbitalsorNot:AbInitioCalculationsandElectronDensityStudies........... 65
10 ConcludingRemarks....................................................................... 67
10.1 ElectronPairsandElectronOctets................................................. 67
References........................................................................................ 68
1 Introduction: The Contributions of G. N. Lewis,
W. Kossel, and I. Langmuir from 1916 to 1923
The developments inthe fields ofatomicphysicsand chemistry that led upto the
publicationsbyG.N.LewisandW.Kosselin1916havebeendescribedbyMingos
[1]. We shall give a brief summary of their contributions to our understanding of
chemical bonding before proceeding to an account of how their ideas have been
developedandmodifiedduringthefollowingdecades.
Both Lewis [2] and Kossel [3] argued on the basis of a shell structure of the
atoms. The first shell may contain one or two electrons and the second and third
from one to eight. The chemical inertness of noble gas atoms, like Ne and Ar,
suggested that atoms with eight electrons in the outmost shell are particularly
stable.Kosselnotedthattheelementsinthegroupprecedingthenoblegases,like
FandCl,haveastrongtendencytoformsinglychargedanionsandthattheatomsin
the group preceding the halogens, like O and S, have a tendency to form doubly
charged anions. On the other hand, the elements in the group following the noble
