Fluxional Organometallic and Coordination Compounds: Physical Organometallic Chemistry, Volume 4 PDF
Preview Fluxional Organometallic and Coordination Compounds: Physical Organometallic Chemistry, Volume 4
Fluxional Organometallic and Coordination Compounds FluxionalOrganometallicandCoordinationCompounds M.Gielen,R.WillemandB.Wrackmeyer (cid:3)C2004JohnWiley&Sons,Ltd ISBN:0-470-85839-7 Physical Organometallic Chemistry EditorialBoard MarcelGielen,FreeUniversityofBrussels,Belgium RudolphWillem,FreeUniversityofBrussels,Belgium BerndWrackmeyer,UniversitätBayreuth,Germany BookspreviouslypublishedinthisSeries Volume1AdvanceApplicationsofNMRtoOrganometallicChemistry Editedby MarcelGielen,FreeUniversityofBrussels,Belgium RudolphWillem,FreeUniversityofBrussels,Belgium BerndWrackmeyer,UniversitätBayreuth,Germany ISBN0471959383 Volume2SolidStateOrganometallicChemistry Editedby MarcelGielen,FreeUniversityofBrussels,Belgium RudolphWillem,FreeUniversityofBrussels,Belgium BerndWrackmeyer,UniversitätBayreuth,Germany ISBN0471979201 Volume3UnusualStructuresandPhysicalPropertiesin OrganometallicChemistry Editedby MarcelGielen,FreeUniversityofBrussels,Belgium RudolphWillem,FreeUniversityofBrussels,Belgium BerndWrackmeyer,UniversitätBayreuth,Germany ISBN0471496359 PHYSICAL ORGANOMETALLIC CHEMISTRY VOLUME 4 Fluxional Organometallic and Coordination Compounds Editedby MARCELGIELEN FreeUniversityofBrussels,Belgium RUDOLPHWILLEM FreeUniversityofBrussels,Belgium BERNDWRACKMEYER UniversitätBayreuth,Germany Copyright(cid:2)C 2004 JohnWiley&SonsLtd,TheAtrium,SouthernGate,Chichester, WestSussexPO198SQ,England Telephone (+44)1243779777 Email(forordersandcustomerserviceenquiries):[email protected] VisitourHomePageonwww.wileyeurope.comorwww.wiley.com AllRightsReserved.Nopartofthispublicationmaybereproduced,storedinaretrievalsystem ortransmittedinanyformorbyanymeans,electronic,mechanical,photocopying,recording, scanningorotherwise,exceptunderthetermsoftheCopyright,DesignsandPatentsAct1988 orunderthetermsofalicenceissuedbytheCopyrightLicensingAgencyLtd,90Tottenham CourtRoad,LondonW1T4LP,UK,withoutthepermissioninwritingofthePublisher. RequeststothePublishershouldbeaddressedtothePermissionsDepartment,JohnWiley& SonsLtd,TheAtrium,SouthernGate,Chichester,WestSussexPO198SQ,England,oremailed [email protected],orfaxedto(+44)1243770620. Thispublicationisdesignedtoprovideaccurateandauthoritativeinformationinregardto thesubjectmattercovered.ItissoldontheunderstandingthatthePublisherisnotengaged inrenderingprofessionalservices.Ifprofessionaladviceorotherexpertassistanceis required,theservicesofacompetentprofessionalshouldbesought. OtherWileyEditorialOffices JohnWiley&SonsInc.,111RiverStreet,Hoboken,NJ07030,USA Jossey-Bass,989MarketStreet,SanFrancisco,CA94103-1741,USA Wiley-VCHVerlagGmbH,Boschstr.12,D-69469Weinheim,Germany JohnWiley&SonsAustraliaLtd,33ParkRoad,Milton,Queensland4064,Australia JohnWiley&Sons(Asia)PteLtd,2ClementiLoop#02-01,JinXingDistripark,Singapore129809 JohnWiley&SonsCanadaLtd,22WorcesterRoad,Etobicoke,Ontario,CanadaM9W1L1 Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprint maynotbeavailableinelectronicbooks. LibraryofCongressCataloging-in-PublicationData Fluxionalorganometallicandcoordinationcompounds/editedbyMarcelGielen,RudolphWillem, BerndWrackmeyer. p. cm.–(Physicalorganometallicchemistry:v.4) Includesbibliographicalreferencesandindex. ISBN0-470-85839-7(cloth:alk.paper) 1.Coordinationcompounds. 2.Organometallicchemistry. 3.Moleculardynamics. 4.Nuclearmagneticresonancespectroscopy. I.Gielen,M.(Marcel),1938- II.Willem,R.(Rudolf) III.Wrackmeyer,Bernd,1947- IV.Series. QD411.F58 2004 541(cid:3).2242–dc22 2004003666 BritishLibraryCataloguinginPublicationData AcataloguerecordforthisbookisavailablefromtheBritishLibrary ISBN0470858397 Typesetin10.5/12ptTimesNewRomanbyTechBooks,NewDelhi,India PrintedandboundinGreatBritainbyMPG,Bodmin,Cornwall Thisbookisprintedonacid-freepaperresponsiblymanufacturedfromsustainableforestry inwhichatleasttwotreesareplantedforeachoneusedforpaperproduction. Contents Contributors . . . . . . . . . . . . . . . . . . . . . xi SeriesPreface . . . . . . . . . . . . . . . . . . . . . xiii Preface . . . . . . . . . . . . . . . . . . . . . . . xv 1 PolyhedralDynamicsandtheJahn–TellerEffect R.BruceKing 1 Introduction . . . . . . . . . . . . . . . . . . . . 1 2 PolyhedronTopology . . . . . . . . . . . . . . . . . 2 3 PolyhedralIsomerizations:MicroscopicModels . . . . . . . 6 3.1 Diamond–Square–DiamondProcesses . . . . . . . . . 6 3.2 GaleDiagrams . . . . . . . . . . . . . . . . . 11 3.3 GenerationofMetallaboraneStructuresbyDiamond–Square– DiamondTransformationsinDeltahedra . . . . . . . . 18 4 PolyhedralIsomerizations:MacroscopicModels . . . . . . . 21 4.1 TopologicalRepresentationsofPolyhedralIsomerizations . . 21 4.2 TopologicalRepresentationsofJahn–TellerDistortions . . 28 5 Acknowledgement . . . . . . . . . . . . . . . . . . 37 6 References . . . . . . . . . . . . . . . . . . . . . 37 2 NMRStudiesofIntramolecularDynamicsinAllylicType Triorganoboranes I.D.GridnevandO.L.Tok 1 Introduction . . . . . . . . . . . . . . . . . . . . 41 2 DiscoveryActivationParametersof[1,3]-BShifts . . . . . . . 42 3 FluxionalLinearPolyunsaturatedAllylboranes . . . . . . . 47 3.1 2,4-Pentadienyl(di-n-propyl)borane . . . . . . . . . . 47 3.2 2,4,6-Heptatrienyl(di-n-propyl)borane . . . . . . . . . 50 4 DynamicBehaviorofCyclicAllylboranes . . . . . . . . . 53 4.1 Dynamic Equilibria Between 2-(Dialkylboryl)methylenecyclo- butanesand1-(Dialkylboryl)cyclobutenes . . . . . . . 53 4.2 Dynamic Properties of Cyclopentadienyl and Pentamethyl- cyclopentadienylDerivativesofBoron . . . . . . . . . 58 4.3 SynthesisandDynamicPropertiesof1-Indenyl(diethyl)borane 58 vi CONTENTS 4.4 DynamicBehaviorofCycloheptadienyl(di-n-propyl) borane . . . . . . . . . . . . . . . . . . . . 60 4.5 Synthesis and Dynamic Properties of Cycloheptatrienyl(di-n- propyl)borane.Equilibriumwith7-(Di-n-propylboryl)norcara- diene . . . . . . . . . . . . . . . . . . . . . 61 4.6 Three Independent Dynamic Processes in the Irontricarbonyl ComplexofCycloheptatrienyl(di-n-propyl)borane . . . . 65 4.7 Cyclooctatetraenyl(di-n-propyl)borane . . . . . . . . . 67 4.8 Sigmatropic Migrations and Thermal Rearrangements in Cyclononatetraenyl(di-n-propyl)borane. Comparison with the DynamicPropertiesofCyclononatetraenyl(trimethyl)tin . . 70 4.9 BorotropicMigrationsinPhenalenyl(di-n-propyl)borane24 . 75 5 DiverseChemoselectivityofCyclicPolyunsaturatedOrganoboranes 77 5.1 ChemicalBehaviorofBorane23 . . . . . . . . . . . 77 5.2 Diverse Chemoselectivity of 9-Cyclopentyl-9-borabarbaralane 54e . . . . . . . . . . . . . . . . . . . . . 79 6 Conclusion . . . . . . . . . . . . . . . . . . . . 81 7 References . . . . . . . . . . . . . . . . . . . . . 81 3 DynamicBehaviorofGroup5and6TransitionMetalComplexes with NMR S.Sakharov 1 Introduction . . . . . . . . . . . . . . . . . . . . 85 2 RotationalIsomerisminAmidoandKetimidoComplexes . . . . 86 2.1 RotationalIsomerisminOxofluoramidoComplexesof Tungsten(VI) . . . . . . . . . . . . . . . . . . 86 2.2 RestrictedM–NR RotationintheDinuclearComplexeswith 2 M 6+ Core(M=W,Mo) . . . . . . . . . . . . . 91 2 2.3 Features of Dynamic Behavior of Amido Cyclopentadienyl ComplexesofGroup5TransitionMetals . . . . . . . . 93 2.4 InternalHinderedRotationofKetimidoLigands . . . . . 95 3 DynamicBehaviorofd0 TransitionMetalComplexeswithn-Donor Two-CenterLigands . . . . . . . . . . . . . . . . . 98 3.1 IsomerizationofFluorocomplexesofGroup5–6with O,N-Two-CenterLigands . . . . . . . . . . . . . 98 3.2 IsomerismofTransitionMetalComplexeswithN, N-Two-centerLigands . . . . . . . . . . . . . . 110 3.3 NatureofBondingofn-DonorTwo-centerLigandsind0 TransitionMetalComplexes . . . . . . . . . . . . 119 3.4 MechanismofInternalHinderedRotationof(cid:2)2-Bound Ligands . . . . . . . . . . . . . . . . . . . . 121 4 Conclusion . . . . . . . . . . . . . . . . . . . . 126 5 References . . . . . . . . . . . . . . . . . . . . . 126 CONTENTS vii 4 ConformationalMobilityinChelatedSquare-planarRh,Ir,Pd,and PtComplexes P.EspinetandJ.A.Casares 1 Introduction . . . . . . . . . . . . . . . . . . . . 131 2 ConformationalChangesinFive-memberMetallacycles . . . . 132 3 ConformationalChangesinSix-memberMetallacycles . . . . . 142 4 ConformationalChangesinFive-orSix-memberMetallacycles InvolvingCoordinatedOlefins . . . . . . . . . . . . . . 152 5 ConformationalChangesinSeven-memberMetallacycles . . . . 154 6 ConformationalChangesinHigherMetallacycles . . . . . . . 156 7 Acknowledegment . . . . . . . . . . . . . . . . . . 158 8 References . . . . . . . . . . . . . . . . . . . . . 158 5 DynamicandKineticAspectsofMetallodrugsbyNMR F.LiandH.Sun 1 Introduction . . . . . . . . . . . . . . . . . . . . 163 2 MethodsofStudybyNMR. . . . . . . . . . . . . . . 164 3 PlatinumAnticancerDrugs . . . . . . . . . . . . . . . 169 3.1 195Pt,15NandInverse[1H,15N]NMRSpectroscopy . . . . 170 3.2 ActivationofPlatinumAnticancerDrugs:Kineticsand EquilibriaofAquation . . . . . . . . . . . . . . 173 3.3 PlatinationofNucleotidesandDNA . . . . . . . . . 176 3.4 InteractionofPlatinumAgentswithAminoAcids,Peptides andProteins . . . . . . . . . . . . . . . . . . 182 4 TitaniumandRutheniumAnticancerAgents . . . . . . . . 185 5 GoldAntiarthriticDrugs . . . . . . . . . . . . . . . 188 6 AntimonyAntiparasiticandBismuthAntiulcerDrugs . . . . . 193 7 VanadiumAntidiabeticMimetics. . . . . . . . . . . . . 197 8 MRIContrastAgents. . . . . . . . . . . . . . . . . 202 9 ConcludingRemarks . . . . . . . . . . . . . . . . . 209 10 Abbreviations . . . . . . . . . . . . . . . . . . . 209 11 Acknowledgements . . . . . . . . . . . . . . . . . 210 12 References . . . . . . . . . . . . . . . . . . . . . 210 6 DynamicsbyEPR:PicosecondtoMicrosecondTimeScales S.VanDoorslaerandG.Jeschke 1 Introduction . . . . . . . . . . . . . . . . . . . . 219 2 ScopeofEPRSpectroscopy . . . . . . . . . . . . . . 221 2.1 NativeParamagneticCenters . . . . . . . . . . . . 221 2.2 SpinLabelsandSpinProbes . . . . . . . . . . . . 222 3 ABriefPrimeronEPRSpectroscopy . . . . . . . . . . . 223 3.1 InteractionsofElectronSpinswithTheirEnvironment . . . 223 3.2 Relaxation . . . . . . . . . . . . . . . . . . . 226 3.3 MeasurementTechniques . . . . . . . . . . . . . 227 viii CONTENTS 4 DetectionofDynamicProcessesbyEPR . . . . . . . . . . 229 4.1 SlowTumbling . . . . . . . . . . . . . . . . . 229 4.2 ExchangeProcesses . . . . . . . . . . . . . . . 231 4.3 DynamicJahn–TellerEffect . . . . . . . . . . . . 231 4.4 ChemicallyInducedDynamicElectronPolarization (CIDEP) . . . . . . . . . . . . . . . . . . . 234 5 ApplicationExample:HowtoCombineDifferentEPR Techniques . . . . . . . . . . . . . . . . . . . . 236 6 Acknowledgements . . . . . . . . . . . . . . . . . 240 7 References . . . . . . . . . . . . . . . . . . . . . 240 7 (cid:2)SRStudiesofMolecularDynamicsinOrganometallics U.A.Jayasooriya 1 Introduction . . . . . . . . . . . . . . . . . . . . 243 2 Muon . . . . . . . . . . . . . . . . . . . . . . 243 3 MuoninMatter . . . . . . . . . . . . . . . . . . . 244 4 Experiment . . . . . . . . . . . . . . . . . . . . 246 5 MuoninaLongitudinalMagneticField . . . . . . . . . . 247 6 Muon–Electron(MuoniumLike)System . . . . . . . . . . 250 7 MolecularDynamics . . . . . . . . . . . . . . . . . 251 8 StudiesofOrganometallics . . . . . . . . . . . . . . . 252 8.1 TetraphenylMetals . . . . . . . . . . . . . . . 252 8.2 BenzeneChromiumTricarbonyl . . . . . . . . . . . 252 8.3 CyclopentadienylManganeseTricarbonyl . . . . . . . 255 8.4 Ruthenocene . . . . . . . . . . . . . . . . . . 256 8.5 Ferrocene . . . . . . . . . . . . . . . . . . . 256 8.6 FerroceneEncapsulatedinZeolite . . . . . . . . . . 261 9 Conclusion . . . . . . . . . . . . . . . . . . . . 263 9 Acknowledgements . . . . . . . . . . . . . . . . . 264 10 References . . . . . . . . . . . . . . . . . . . . . 264 8 ProtonDynamicsinSolids:VibrationalSpectroscopy withNeutrons F.Fillaux 1 Introduction . . . . . . . . . . . . . . . . . . . . 267 2 VibrationalSpectroscopyTechniques . . . . . . . . . . . 269 2.1 SomeDefinitions . . . . . . . . . . . . . . . . 269 2.2 OpticalTechniques . . . . . . . . . . . . . . . . 270 2.3 NeutronScatteringTechniques . . . . . . . . . . . 271 2.4 PotassiumHydrogenBistrifluoroacetate . . . . . . . . 276 3 VibrationalDynamicsofProtonsinSolids . . . . . . . . . 278 3.1 Force-FieldCalculations:NormalversusLocalized Modes . . . . . . . . . . . . . . . . . . . . 278 3.2 TheProtonCrystalModel . . . . . . . . . . . . . 280 CONTENTS ix 4 Tunnelling . . . . . . . . . . . . . . . . . . . . . 282 4.1 ProtonTransfer . . . . . . . . . . . . . . . . . 282 4.2 RotationalTunnelling . . . . . . . . . . . . . . . 285 5 Conclusions . . . . . . . . . . . . . . . . . . . . 301 6 References . . . . . . . . . . . . . . . . . . . . . 302 Index . . . . . . . . . . . . . . . . . . . . . . . . 305 Contributors R Bruce King, Department of Chemistry, University of Georgia, Athens, Georgia30602,USA IlyaDGridnev,COELaboratory,DepartmentofChemistry,GraduateSchool ofScience,TohokuUniversity,Sendai980-8578,Japan Oleg L Tok, Anorganische Chemie II, University of Bayreuth, D-95440 Bayreuth,Germany Sergei G Sakharov, Kurnakov Institute of General and Inorganic Chemistry, RussianAcademyofSciences,Leninskiipr.31,Moscow119991,Russia Pablo Espinet, Departamento de Quimica Inorganica, Universidad de Valladolid,E-47005Valladolid,Spain Juan A Casares, Departamento de Quimica Inorganica, Universidad de Valladolid,E-47005Valladolid,Spain Hongzhe Sun, Department of Chemistry and Open Laboratory of Chemical Biology,UniversityofHongKong,PokfulamRoad,HongKong FeiLi,DepartmentofChemistryandOpenLaboratoryofChemicalBiology, UniversityofHongKong,PokfulamRoad,HongKong Sabine Van Doorslaer, SIBAC Laboratorium, Universiteit Antwerpen – De- partmentNatuurkunde,Universiteitsplein1,B-2610Wilrijk,Belgium Gunnar Jeschke, Max-Planck-Institute for Polymer Research, Postfach 3148, D-55021Mainz,Germany Upali Jayasooriya, School of Chemical Sciences, University of East Anglia, Norwich,UK Françoise Fillaux, Laborotoire de Spectrochimie Infrarouge et Raman, CNRS, 2rueHenryDunant,Thiaise,France
The list of books you might like
