Introduction to Coordination Chemistry (Inorganic Chemistry: A Textbook Series)

307 Pages·2010·5.23 MB·English

by  Geoffrey Alan Lawrance

P1:OTE/OTE/SPH P2:OTE
FM JWBK420-Lawrance November16,2009 8:45 Printer:YettoCome
Introduction to
Coordination Chemistry
Geoffrey A. Lawrance
University of Newcastle, Callaghan, NSW, Australia
A John Wiley and Sons, Ltd., Publication

P1:OTE/OTE/SPH P2:OTE
FM JWBK420-Lawrance November16,2009 8:45 Printer:YettoCome
Introduction to Coordination Chemistry
P1:OTE/OTE/SPH P2:OTE
FM JWBK420-Lawrance November16,2009 8:45 Printer:YettoCome
Inorganic Chemistry
A Wiley Series of Advanced Textbooks
ISSN: 1939-5175
Editorial Board
David Atwood, University of Kentucky, USA
Bob Crabtree, Yale University, USA
Gerd Meyer, University of Cologne, Germany
Derek Woollins, University of St. Andrews, UK
Previously Published Books in this Series
Chirality in Transition Metal Chemistry
Hani Amouri & Michel Gruselle; ISBN: 978-0-470-06054-4
Bioinorganic Vanadium Chemistry
Dieter Rehder; ISBN: 978-0-470-06516-7
Inorganic Structural Chemistry, Second Edition
Ulrich Mu¨ller; ISBN: 978-0-470-01865-1
Lanthanide and Actinide Chemistry
Simon Cotton; ISBN: 978-0-470-01006-8
Mass Spectrometry of Inorganic and Organometallic Compounds:
Tools – Techniques – Tips
William Henderson & J. Scott McIndoe; ISBN: 978-0-470-85016-9
Main Group Chemistry, Second Edition
A. G. Massey; ISBN: 978-0-471-49039-5
Synthesis of Organometallic Compounds: A Practical Guide
Sanshiro Komiya; ISBN: 978-0-471-97195-5
Chemical Bonds: A Dialog
Jeremy Burdett; ISBN: 978-0-471-97130-6
Molecular Chemistry of the Transition Elements: An Introductory Course
Franc¸ois Mathey & Alain Sevin; ISBN: 978-0-471-95687-7
Stereochemistry of Coordination Chemistry
Alexander Von Zelewsky; ISBN: 978-0-471-95599-3
Bioinorganic Chemistry: Inorganic Elements in the Chemistry of Life – An Introduction
and Guide
Wolfgang Kaim; ISBN: 978-0-471-94369-3
For more information on this series see: www.wiley.com/go/inorganic
P1:OTE/OTE/SPH P2:OTE
FM JWBK420-Lawrance November16,2009 8:45 Printer:YettoCome
Introduction to
Coordination Chemistry
Geoffrey A. Lawrance
University of Newcastle, Callaghan, NSW, Australia
A John Wiley and Sons, Ltd., Publication
P1:OTE/OTE/SPH P2:OTE
FM JWBK420-Lawrance November16,2009 8:45 Printer:YettoCome
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Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Preamble . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi
1 TheCentralAtom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 KeyConceptsinCoordinationChemistry . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 AWho’sWhoofMetalIons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2.1 Commonersand‘Uncommoners’ . . . . . . . . . . . . . . . . . . . . . . . 5
1.2.2 RedefiningCommoners . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3 MetalsinMolecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.3.1 MetalsintheNaturalWorld . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.3.2 MetalsinContrivedEnvironments . . . . . . . . . . . . . . . . . . . . . . . 11
1.3.3 NaturalorMade-to-MeasureComplexes . . . . . . . . . . . . . . . . . . . . 12
1.4 TheRoadAhead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
ConceptKeys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
FurtherReading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2 Ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.1 Membership:BeingaLigand . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.1.1 WhatMakesaLigand? . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.1.2 MakingAttachments–Coordination . . . . . . . . . . . . . . . . . . . . . . 16
2.1.3 PuttingtheBiteonMetals–Chelation . . . . . . . . . . . . . . . . . . . . . 17
2.1.4 DoILookBigonThat?–ChelateRingSize . . . . . . . . . . . . . . . . . . 22
2.1.5 DifferentTribes–DonorGroupVariation . . . . . . . . . . . . . . . . . . . 23
2.1.6 LigandswithMoreBite–Denticity . . . . . . . . . . . . . . . . . . . . . . 24
2.2 MonodentateLigands–TheSimpleType . . . . . . . . . . . . . . . . . . . . . . . 26
2.2.1 BasicBinders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.2.2 AminesAin’tAmmines–LigandFamilies . . . . . . . . . . . . . . . . . . . 27
2.2.3 MeetingMoreMetals–BridgingLigands . . . . . . . . . . . . . . . . . . . 27
2.3 GreedisGood–PolydentateLigands . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.3.1 TheSimpleChelate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.3.2 MoreTeeth,StrongerBite–Polydentates . . . . . . . . . . . . . . . . . . . 31
2.3.3 Many-ArmedMonsters–IntroducingLigandShape . . . . . . . . . . . . . . 32
2.4 PolynucleatingSpecies–MolecularBigamists . . . . . . . . . . . . . . . . . . . . 33
2.4.1 WhenOneisNotEnough . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.4.2 VivelaDifference–Mixed-metalComplexation . . . . . . . . . . . . . . . . 34
2.4.3 Supersized–BindingtoMacromolecules . . . . . . . . . . . . . . . . . . . 36
2.5 ASeparateRace–OrganometallicSpecies . . . . . . . . . . . . . . . . . . . . . . 36
ConceptKeys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
FurtherReading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
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vi Contents
3 Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.1 TheCentralMetalIon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.2 Metal–LigandMarriage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.2.1 TheCoordinateBond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.2.2 TheFoundationofCoordinationChemistry . . . . . . . . . . . . . . . . . . 42
3.2.3 ComplexShape–NotJustAnyWhichWay . . . . . . . . . . . . . . . . . . 45
3.3 HoldingOn–TheNatureofBondinginMetalComplexes . . . . . . . . . . . . . . . 49
3.3.1 AnIonicBondingModel–IntroducingCrystalFieldTheory . . . . . . . . . . 53
3.3.2 ACovalentBondingModel–EmbracingMolecularOrbitalTheory . . . . . . . 57
3.3.3 LigandFieldTheory–MakingCompromises . . . . . . . . . . . . . . . . . 62
3.3.4 BondingModelsExtended . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3.4 Coupling–PolymetallicComplexes . . . . . . . . . . . . . . . . . . . . . . . . . 73
3.5 MakingChoices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.5.1 Selectivity–OfalltheMoleculesinalltheWorld,WhyThisOne? . . . . . . . 75
3.5.2 Preferences–DoYouLikeWhatILike? . . . . . . . . . . . . . . . . . . . . 75
3.5.3 ComplexLifetimes–Together,Forever? . . . . . . . . . . . . . . . . . . . . 77
3.6 ComplexationConsequences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
ConceptKeys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
FurtherReading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
4 Shape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
4.1 GettinginShape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
4.2 FormsofComplexLife–CoordinationNumberandShape . . . . . . . . . . . . . . 86
4.2.1 OneCoordination(ML) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
4.2.2 TwoCoordination(ML ) . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
2
4.2.3 ThreeCoordination(ML ) . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3
4.2.4 FourCoordination(ML ) . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4
4.2.5 FiveCoordination(ML ) . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
5
4.2.6 SixCoordination(ML ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
6
4.2.7 HigherCoordinationNumbers(ML toML ) . . . . . . . . . . . . . . . . . 98
7 9
4.3 InfluencingShape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4.3.1 MetallicGenetics–MetalIonInfluences . . . . . . . . . . . . . . . . . . . . 101
4.3.2 MouldingaRelationship–LigandInfluences . . . . . . . . . . . . . . . . . 103
4.3.3 ChameleonComplexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
4.4 Isomerism–Real3DEffects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
4.4.1 IntroducingStereoisomers. . . . . . . . . . . . . . . . . . . . . . . . . . . 106
4.4.2 Constitutional(Structural)Isomerism . . . . . . . . . . . . . . . . . . . . . 106
4.4.3 Stereoisomerism:inPlace–PositionalIsomers;inSpace–OpticalIsomers . . . 109
4.4.4 What’sBest?–IsomerPreferences . . . . . . . . . . . . . . . . . . . . . . 113
4.5 SophisticatedShapes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.5.1 CompoundsofPolydentateLigands . . . . . . . . . . . . . . . . . . . . . . 116
4.5.2 EncapsulationCompounds . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.5.3 Host–GuestMolecularAssemblies . . . . . . . . . . . . . . . . . . . . . . 121
4.6 DefiningShape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
ConceptKeys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
FurtherReading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
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Contents vii
5 Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
5.1 TheMakingsofaStableRelationship . . . . . . . . . . . . . . . . . . . . . . . . . 125
5.1.1 BeddedDown–ThermodynamicStability . . . . . . . . . . . . . . . . . . . 125
5.1.2 FactorsInfluencingStabilityofMetalComplexes . . . . . . . . . . . . . . . 127
5.1.3 OverallStabilityConstants . . . . . . . . . . . . . . . . . . . . . . . . . . 138
5.1.4 UndergoingChange–KineticStability . . . . . . . . . . . . . . . . . . . . 141
5.2 Complexation–WillItLast? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
5.2.1 ThermodynamicandKineticStability . . . . . . . . . . . . . . . . . . . . . 143
5.2.2 KineticRateConstants . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
5.2.3 LabilityandInertnessinOctahedralComplexes . . . . . . . . . . . . . . . . 145
5.3 Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
5.3.1 ANewPartner–Substitution . . . . . . . . . . . . . . . . . . . . . . . . . 147
5.3.2 ANewBody–StereochemicalChange . . . . . . . . . . . . . . . . . . . . 155
5.3.3 ANewFace–Oxidation–Reduction . . . . . . . . . . . . . . . . . . . . . . 160
5.3.4 ANewSuit–Ligand-centredReactions . . . . . . . . . . . . . . . . . . . . 169
ConceptKeys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
FurtherReading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
6 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
6.1 MolecularCreation–WaystoMakeComplexes . . . . . . . . . . . . . . . . . . . . 173
6.2 CoreMetalChemistry–PeriodicTableInfluences . . . . . . . . . . . . . . . . . . . 173
6.2.1 sBlock:AlkaliandAlkalineEarthMetals . . . . . . . . . . . . . . . . . . . 173
6.2.2 pBlock:MainGroupMetals . . . . . . . . . . . . . . . . . . . . . . . . . 174
6.2.3 dBlock:TransitionMetals . . . . . . . . . . . . . . . . . . . . . . . . . . 175
6.2.4 fBlock:InnerTransitionMetals(LanthanoidsandActinoids) . . . . . . . . . . 176
6.2.5 BeyondNaturalElements . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
6.3 ReactionsInvolvingtheCoordinationShell . . . . . . . . . . . . . . . . . . . . . . 179
6.3.1 LigandSubstitutionReactionsinAqueousSolution. . . . . . . . . . . . . . . 179
6.3.2 SubstitutionReactionsinNonaqueousSolvents . . . . . . . . . . . . . . . . 184
6.3.3 SubstitutionReactionswithoutusingaSolvent . . . . . . . . . . . . . . . . . 186
6.3.4 ChiralComplexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
6.3.5 CatalysedReactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
6.4 ReactionsInvolvingtheMetalOxidationState . . . . . . . . . . . . . . . . . . . . 190
6.5 ReactionsInvolvingCoordinatedLigands . . . . . . . . . . . . . . . . . . . . . . . 194
6.5.1 Metal-directedReactions . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
6.5.2 ReactionsofCoordinatedLigands . . . . . . . . . . . . . . . . . . . . . . . 197
6.6 OrganometallicSynthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
ConceptKeys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
FurtherReading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
7 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
7.1 FindingWaystoMakeComplexesTalk–InvestigativeMethods . . . . . . . . . . . . 209
7.2 GettingPhysical–MethodsandOutcomes . . . . . . . . . . . . . . . . . . . . . . 210
7.3 ProbingtheLifeofComplexes–UsingPhysicalMethods . . . . . . . . . . . . . . . 214
7.3.1 PeakPerformance–IllustratingSelectedPhysicalMethods . . . . . . . . . . . 216
7.3.2 PrettyinRed?–ColourandtheSpectrochemicalSeries . . . . . . . . . . . . 220