Table Of ContentStructure and Bonding 167
Series Editor: D.M.P. Mingos
Stuart A. Macgregor
Odile Eisenstein Editors
Computational
Studies in
Organometallic
Chemistry
167
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 with chemical structure and bonding. The scope of the series spans the
entirePeriodicTableandaddressesstructureandbondingissuesassociatedwithallof
the elements. It also focuses attention on new and developing areas of modern
structural and theoretical chemistry such as nanostructures, molecular electronics,
designed molecular solids, surfaces, metal clusters and supramolecular structures.
Physicalandspectroscopictechniquesusedtodetermine,examineandmodelstruc-
turesfallwithinthepurviewofStructureandBondingtotheextentthatthefocusison
the scientific results obtained and not on specialist information concerning the
techniques themselves. Issues associated with the development of bonding models
and generalizations that illuminate the reactivity pathways and rates of chemical
processesarealsorelevant
Theindividualvolumesintheseriesarethematic.Thegoalofeachvolumeistogive
thereader,whetheratauniversityorinindustry,acomprehensiveoverviewofanarea
where new insights are emerging that are ofinterest toa larger scientific audience.
Thus each review within the volume criticallysurveysone aspect ofthattopic and
placesitwithinthecontextofthevolumeasawhole.Themostsignificantdevelop-
mentsofthelast5to10yearsshouldbepresentedusingselectedexamplestoillustrate
the principles discussed. A description of the physical basis of the experimental
techniquesthathavebeenusedtoprovidetheprimarydatamayalsobeappropriate,
ifithasnotbeencoveredindetailelsewhere.Thecoverageneednotbeexhaustivein
data, but should rather be conceptual, concentrating on the new principles being
developed that will allow the reader, who is not a specialistinthe areacovered,to
understandthedatapresented.Discussionofpossiblefutureresearchdirectionsinthe
areaiswelcomed.
Reviewarticlesfortheindividualvolumesareinvitedbythevolumeeditors.
In references Structure and Bonding is abbreviated Struct Bond and is cited as a
journal.
Moreinformationaboutthisseriesathttp://www.springer.com/series/430
Stuart A. Macgregor (cid:1) Odile Eisenstein
Editors
Computational Studies in
Organometallic Chemistry
With contributions by
(cid:3) (cid:3) (cid:3)
N.M.S. Almeida F.M. Bickelhaupt K.J.T. Carr
(cid:3) (cid:3) (cid:3) (cid:3)
O. Eisenstein D.H. Ess S.J. Gustafson J. Jover
C.R.King(cid:3) Z.Lin(cid:3) A.Lledo´s(cid:3) S.A.Macgregor(cid:3) F.Maseras(cid:3)
(cid:3) (cid:3) (cid:3)
D. McKay R.G. McKinlay C.L. McMullin
(cid:3) (cid:3) (cid:3) (cid:3)
M.J. Paterson L. Perrin G. Ujaque P. Vidossich
L.P. Wolters
Editors
StuartA.Macgregor OdileEisenstein
InstituteofChemicalSciences InstitutCharlesGerhardt
Heriot-WattUnversity UMR5253-CNRS-UM-ENSCM
Edinburgh Universite´deMontpellier
UnitedKingdom PlaceE.Bataillon
Montpellier
France
ISSN0081-5993 ISSN1616-8550 (electronic)
StructureandBonding
ISBN978-3-319-31636-9 ISBN978-3-319-31638-3 (eBook)
DOI10.1007/978-3-319-31638-3
LibraryofCongressControlNumber:2016939982
#SpringerInternationalPublishingSwitzerland2016
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Preface
IncompilingthisvolumeComputationalStudiesinOrganometallicChemistry,we
haveinvitedsevencontributionsthatshowcasehowstate-of-the-artquantummeth-
ods can address practical problems in molecular inorganic chemistry and provide
insights into the factors that underpin the behaviour of these systems. In the first
chapter Perrin, Carr, McKay, McMullin, Macgregor and Eisenstein present a
description of current practices for the exploration of reaction mechanisms. This
is further illustrated by Lin’s chapter on the structure and reactivity of boryl
complexes. Jover and Maseras then describe the use of QM/MM methods in
modelling selectivity, and Vidossich, Lledo´s and Ujaque detail how molecular
dynamic simulations have been applied in this area. Almeida, McKinlay and
Paterson describewhatis nowpossibleinmodellingexcitedstates andassociated
reactivity. Tools to understand the origin of energy barriers are the focus of the
chapterspresentedbyWoltersandBickelhauptwhooutlinetheenergydecomposi-
tionanalysis(EDA)approach,whileKing,GustafonandEssapplythistechniqueto
thetopicofC–Hactivation.
As well as thanking all the contributing authors, the editors would like to
dedicatethisvolumetothememoryofTomZiegler,atruepioneerinthedevelop-
mentofmethodsandtheirapplicationsininorganicchemistry.
Stockholm,Sweden StuartA.Macgregor
4September2015 OdileEisenstein
v
ThiSisaFMBlankPage
Contents
ModellingandRationalizingOrganometallicChemistrywith
Computation:WhereAreWe?................................................. 1
LionelPerrin,KevinJ.T.Carr,DavidMcKay,ClaireL.McMullin,
StuartA.Macgregor,andOdileEisenstein
ReactivitiesandElectronicPropertiesofBorylLigands.................... 39
ZhenyangLin
QM/MMCalculationsonSelectivityinHomogeneousCatalysis........... 59
Jesu´sJoverandFeliuMaseras
RealisticSimulationofOrganometallicReactivityinSolution
byMeansofFirst-PrinciplesMolecularDynamics .......................... 81
PietroVidossich,Agust´ıLledo´s,andGregoriUjaque
ComputationofExcitedStatesofTransitionMetalComplexes........... 107
NunoM.S.Almeida,RussellG.McKinlay,andMartinJ.Paterson
d10-ML Complexes:Structure,Bonding,andCatalyticActivity ......... 139
2
LandoP.WoltersandF.MatthiasBickelhaupt
TheElectronicsofCHActivationbyEnergyDecompositionAnalysis:
FromTransitionMetalstoMain-GroupMetals............................ 163
ClintonR.King,SamanthaJ.Gustafson,andDanielH.Ess
Index............................................................................ 179
vii
StructBond(2016)167:1–38
DOI:10.1007/430_2015_176
#SpringerInternationalPublishingSwitzerland2015
Publishedonline:11September2015
Modelling and Rationalizing Organometallic
Chemistry with Computation: Where Are
We?
LionelPerrin,KevinJ.T.Carr,DavidMcKay,ClaireL.McMullin,
StuartA.Macgregor,andOdileEisenstein
Abstract Inthischapter,aperspectiveonhowthefieldofappliedcomputational
organometallic chemistry has developed since the mid-1980s is presented. We
describe the way in which the modelling of chemical systems has evolved over
time,usingmetallocene chemistryasanexample,andhighlightthesuccessesand
limitationsofsimplemodelsthatweremandatoryintheearlydaysofthediscipline.
Anumberofmorerecentcasestudiesarethenpresentedwherethefullexperimental
systemisnowemployedandamorequantitativeoutcomeissought.Thisincludes
examplesfromtheCe-mediatedhydrogenationofpyridine,Rh-catalysedC–Hbond
activationandfunctionalization,Pd-catalysedazidocarbonylationandphenyliodide
activationatRu(II)complexes.Weconcludewithourtakeonthetitlequestion.
Keywords Bond activation (cid:1) Computational chemistry (cid:1) DFT (cid:1) Dispersion
correction(cid:1)Mechanism(cid:1)Modelling(cid:1)Organometallics(cid:1)Selectivity
L.Perrin(*)
Universite´ClaudeBernardLyon1,CNRSUMR5246,InstitutdeChimieetBiochimie
Mole´culairesetSupramole´culaires,CPELyon,43Boulevarddu11Novembre1918,69622
Villeurbannecedex,France
e-mail:[email protected]
K.J.T.Carr,C.L.McMullin,andS.A.Macgregor(*)
InstituteofChemicalSciences,Heriot-WattUniversity,EdinburghEH144AS,UK
e-mail:[email protected]
D.McKay
Presentaddress;SchoolofChemistry,UniversityofSt.Andrews,NorthHaugh,St.Andrews
KY169ST,UK
InstituteofChemicalSciences,Heriot-WattUniversity,EdinburghEH144AS,UK
O.Eisenstein(*)
InstitutCharlesGerhardt,CNRSUMR5253,Universite´deMontpellier,PlaceE.Bataillon,
34095Montpellier,France
e-mail:[email protected]
2 L.Perrinetal.
Contents
1 Introduction................................................................................... 2
2 TheDevelopmentofChemicalModels..................................................... 3
2.1 TheCaseofMetalloceneDerivatives................................................. 4
3 CurrentPractice:CaseStudies............................................................... 13
3.1 HydrogenationofPyridine............................................................. 14
3.2 C–HBondActivationandFunctionalizationatRhandIrHalf-SandwichComplexes 17
3.3 QuantifyingBarrierstoPh–IBondActivationatPd(0)andRu(II)–Phosphine
Complexes.............................................................................. 24
4 Conclusions................................................................................... 32
References........................................................................................ 33
1 Introduction
Computationalchemistryhasmadeasustainedcontributiontotheunderstandingof
chemical reactions. In 1965, three landmark communications in the Journal of the
AmericanChemicalSocietyfromWoodwardandHoffmannmarkedaparadigmshift
inthewaythatchemistsapproachedtheproblemofmechanismandreactivity.These
threepaperswhichdealtwith,inturn,electrocyclicreactions[1],cycloadditions[2]
and sigmatropic rearrangements [3] laid down the fundamental bases for the theo-
retical treatment of concerted reactions and culminated in the formulation of the
Woodward–Hoffmannrules[4].Thiswayoflinkingexperimentandtheoryopened
thedoorfortheapplicationofqualitativemethodsbyFukui,Hoffmannandothersin
theareasoforganic,inorganicandthenorganometallicchemistry.Intheyearsupto
theawardoftheNobelPrize,sharedwithFukui,in1981[5],Hoffmanndeveloped
theconceptoftheisolobalanalogythathighlightsthecommonalitiesthatexistright
acrossthesefields[6].Runninginparallelthroughoutthisperiodwerethedevelop-
mentsintheoreticalchemistrychampionedbyPopleandKohnthatwereultimately
recognizedwiththe award ofthe Nobel Prizein 1998. The qualitative approachof
Hoffmann and Fukui emphasized the underlying electronic structure of functional
groups and often exploited symmetry and topological arguments to account for
patternsinstructureandreactivity.Attheotherextreme,bothwavefunctiontheory
anddensityfunctionaltheory(DFT)offeredthepromiseofquantitativeaccuracy.
Inrecentdecades,computationalchemistryasappliedtoorganometallicchemistry
hasfurtherbuiltontheideasofHoffmannandhasincreasinglylookedtoexploitthe
sophisticatedtoolsdevelopedandmadeavailablebytheoreticalchemists[7,8].Itseems
thatwearenowatthepointwherecomputationalchemistrycanprovideaquantitative
representation of chemical reactivity. This, coupled to the fundamental underlying
principles derived from earlier work and modern techniques of electronic structure
analysis,isseeminglyleadingustowardsthe“HolyGrail”ofpredictingreactivityina
quantitativewaythatmaytrulyinformthedesignofexperimentalsystems.
In this chapter, we present our perspective on how the field of applied compu-
tational organometallic chemistry has developed since the mid-1980s. Unless
