Elsevier S & T

The Chemistry of Pincer Compounds

Morales-Morales, David; Jensen, Craig G.M.

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Table of contents

Cover
Table of Contentsvii
Prefacexv
Chapter 1 Organometallic pincer-type complexes: recent applications in synthesis and catalysis1
1.1 Introduction1
1.2 Preparation of Pincer Palladacycles2
1.2.1 General Remarks2
1.2.2 The Chloropalladation Reaction Path4
1.3 Structural Aspects6
1.3.1 Solution Phase Studies6
1.3.2 Mass Spectrometry Studies7
1.3.3 Solid-State Studies9
1.4 Pincers as Catalyst Precursors for Cross-Coupling Reactions Involving Aryl Substrates9
1.4.1 General Remarks9
1.4.2 Heck Coupling12
1.4.3 Suzuki Cross-Coupling18
1.4.4 Sonogashira Coupling20
1.5 Conclusions and Trends21
Chapter 2 Synthesis and transformation of allyl- and allenyl-metal species by pincer complex catalys25
2.1 Introduction25
2.2 Palladium-Catalyzed Allylation of Electrophiles26
2.2.1 Pincer Complex-Catalyzed Coupling of Allyl Stannanes with Aldehydes27
2.2.2 Trifluoro(allyl)borate as Allylating Agent28
2.2.3 Application of Chiral Pincer Complex Catalysts for Allylation of Sulfonimines29
2.2.4 Mechanism of the Pincer Complex-Catalyzed Electrophilic Allylic Substitution30
2.3 Pincer Complex-Catalyzed Synthesis of Organometallic Compounds32
2.3.1 Synthesis of Allylboronic Acids and Allyl Boronates32
2.3.2 Pincer Complex-Catalyzed Synthesis of Allyl Stannanes34
2.3.3 Stannylation of Propargylic Substrates35
2.3.4 Synthesis of Allenyl Silanes Using Pincer Complex Catalysis36
2.3.5 Phenylselenation of Organohalides37
2.3.6 Mechanistic Aspects of the Pincer Complex-Catalyzed Organometallic Group Transfer Processes37
2.4 Conclusions and Outlook41
Chapter 3 Chiral pincer complexes and their application to asymmetric synthesis45
3.1 Introduction45
3.2 The Synthesis of Chiral Nonracemic Pincer Complexes Containing Anionic Terdentate Ligands45
3.2.1 NCN Complexes46
3.2.2 NNN Complexes56
3.2.3 PCP Complexes59
3.2.4 SCS Complexes61
3.2.5 Mixed Donor Complexes62
3.2.6 Reactions of Chiral Pincers62
3.3 The Application of Pincer Complexes to Asymmetric Synthesis63
3.3.1 Imine Alkylation64
3.3.2 Allylation, Propargylation and Allenylation64
3.3.3 The Diels–Alder and Aldol Reactions67
3.3.4 The Reaction of Activated Isonitriles with Aldehydes68
3.3.5 The Michael Reaction71
3.3.6 Reduction Reactions73
3.3.7 Miscellaneous Reactions74
Chapter 4 Desulfurization catalyzed by nickel PCP-pincer compounds79
4.1 Introduction79
4.2 HDS Catalysts80
4.2.1 Coordination Modes of Thiophenic Moieties80
4.2.2 Metal Insertion into C−S Bonds81
4.2.3 Catalytic Homogeneous Desulfurization82
4.3 Desulfurization Catalyzed by Nickel PCP-Pincer Compounds82
Chapter 5 Pincer systems as models for the activation of strong bonds: scope and mechanism87
5.1 Introduction87
5.2 CŠH vs CŠC Bond Oxidative Addition in PCX-Type Systems87
5.2.1 Insertion into a Strong C−C Bond in Solution: C−C vs C−H Activation88
5.2.2 The Methylene Transfer Reaction98
5.3 Metal Insertion into Unstrained CŠO Bonds101
5.4 Summary103
Chapter 6 ‘Pincer’-carbene complexes107
6.1 Introduction107
6.2 Pincer-Carbene Complexes of Metals from the Platinum Group108
6.2.1 Palladium Pincer-Carbene Complexes108
6.2.2 Rhodium and Ruthenium Pincer-Carbene Complexes113
6.3 Pincer-Carbene Complexes of Other Metals118
6.3.1 Pincer-Carbene Complexes of Fe, Co and Early Transition Metals118
Chapter 7 Pincer complexes derived from benzimidazolin-2-ylidene ligands125
7.1 Synthesis of Complexes with Benzimidazolin-2-ylidene Ligands125
7.2 Complexes with N-allyl-Functionalized Benzimidazolin-2-ylidene Ligands126
7.3 Coordination Chemistry of the N,N'-diallyl-Functionalized Benzimidazolin-2-ylidene Ligand at Iri127
7.4 Pincer Complexes with N,N’-Heteroatom-Functionalized Benzimidazolin-2-Ylidene Ligands128
7.5 Synthesis of Pincer Complexes with Tridentate Dicarbene Ligands130
7.6 NMR Studies on Dicarbene Pincer Complexes134
Chapter 8 Pincer complexes of N-heterocyclic carbenes. Potential uses as pharmaceuticals139
8.1 Introduction139
8.1.1 N-heterocyclic Carbenes139
8.2 Silver NHC-pincer complexes140
8.2.1 Silver Antimicrobials140
8.2.2 Synthesis of Pyridine-Based Silver NHC-Pincer Complexes141
8.2.3 Antimicrobial Activity of Silver NHC-Pincer Complexes142
8.3 Rhodium NHC-Pincer Model Complexes145
8.3.1 Synthesis of Rhodium NHC-Pincer Complexes145
8.3.2 Ligand Modification for Targeting147
8.4 Conclusions149
Chapter 9 The chemistry of PCP pincer phosphinite transition metal complexes151
9.1 Introduction151
9.2 Synthesis of the Ligands152
9.3 Synthesis and Reactivity of Transition Metal Phosphinite PCP Pincer Complexes153
9.3.1 Palladium Complexes153
9.3.2 Iridium complexes163
9.3.3 Rhodium Complexes170
9.3.4 Ruthenium Complexes171
9.3.5 Platinum Complexes174
9.3.6 Nickel Complexes175
9.4 Conclusions177
Chapter 10 Nitrogen-based pincers: a versatile platform for organometallic chemistry181
10.1 Introduction181
10.2 Lithium Complexes182
10.3 Early Transition Metals185
10.3.1 Titanium185
10.3.2 Molybdenum186
10.3.3 Tungsten187
10.4 Mid-Transition Metals188
10.4.1 Group 7 (MnŠRe)188
10.4.2 Group 8 (Fe−Os)190
10.5 Late Transition Metals194
10.5.1 Cobalt194
10.5.2 Rhodium195
10.5.3 Iridium204
10.5.4 Group 10 (Ni−Pt)207
10.5.5 Group 11 (Cu−Au)220
10.5.6 Group 12 (Zn−Hg)226
10.6 Conclusions228
Chapter 11 SŠPŠS and SŠCŠS pincer ligands in coordination chemistry and catalysis235
11.1 Introduction235
11.2 SŠPŠS Pincer Ligands235
11.2.1 Bis(phosphinosulfide)phosphinines235
11.2.2 Bis(thioether)phosphines251
11.3 SŠCŠS (and Se~C~Se) Pincer Ligands251
11.3.1 Thioether (N1) and Related Selenoether (N2) Derivatives251
11.3.2 Thioamide (E) and Phosphine Sulfide (F) Derivatives262
11.3.3 Anion (G) and Dianion (H) of the Bis-(diphenylphosphinosulfide)-methane262
11.4 Conclusion268
Chapter 12 Pincer ligand complexes with unusual atoms and molecular backbones273
12.1 Introduction273
12.1.1 From Ylides to Pincers273
12.2 Intra- vs. Intermolecular CŠH Activation275
12.3 PNP Pincer Ligand Backbone277
12.4 Pincer Carbene Complexes278
12.4.1 Endocyclic Pincer Carbenes278
12.4.2 Cycloheptatriene as Ligand Backbone280
12.5 Conclusion284
Chapter 13 Rigid PNP pincer ligands and their transition metal complexes287
13.1 Introduction287
13.2 Ligand Synthesis288
13.2.1 Approaches to CŠP Bond Construction288
13.2.2 Approaches to the Diarylamine Precursors289
13.3 Group 4 Metals: Multiple MetalŠCarbon Bonds290
13.3.1 Synthesis of Zr Alkylidenes291
13.3.2 Synthesis of Ti Alkylidenes and Related Compounds291
13.4 Ruthenium: CO Abstraction293
13.5 Group 9 Metal Chemistry294
13.5.1 Intramolecular NŠH, NŠC, and CŠH Oxidative Addition Reactions294
13.5.2 Competitive C−H vs. C-Hal Oxidative Addition Reactions of Haloarenes296
13.5.3 Catalytic Alkyne Dimerization298
13.5.4 PNP Complexes of Cobalt299
13.6 Group 10 Chemistry300
13.6.1 Synthesis of Various (PNP)MX Complexes300
13.6.2 Catalytic Applications of (PNP)MX304
13.7 Copper Complexes306
13.8 Summary306
Chapter 14 Pincer, chelate and spirocyclic metal carbene complexes from bis(iminophosphorano)methane311
14.1 Introduction and Overview311
14.2 The Beginning: Pincers of Early Transition Metals315
14.2.1 Structures318
14.2.2 Reaction Chemistry of the Group 4 Pincers319
14.2.3 The Nature of the M=C Bond: Theory323
14.2.4 Other Early Transition Metals324
14.3 Bis-Ligated Complexes325
14.4 Early Metal-Bridging Carbenes326
14.5 Main Group Metal Complexes328
14.5.1 Aluminum328
14.5.2 Zinc331
14.5.3 Other Main Group Metals332
14.6 Platinum Group Metals332
14.6.1 A Triple Carbene Pincer334
14.6.2 Orthometallation and Rearrangements335
14.7 Bimetallic Spirocycles336
14.7.1 Synthesis and Characterization336
14.7.2 Reactions of Bimetallic Complexes338
14.7.3 Reactivity of the Lithiated Spirocycle339
14.7.4 A Ketene Complex340
14.7.5 The Reactivity of the Ketene341
14.8 Summary342
Chapter 15 Pincer and chelate carbodiphosphorane complexes of noble metals347
15.1 Introduction347
15.2 Background348
15.3 Metal Complexes of Hexaphenylcarbodiphosphorane349
15.3.1 Synthesis349
Chapter 16 Hypervalent organotin, aluminium, antimony and bismuth Y,C,Y-chelate complexes357
16.1 Introduction357
16.2 Organotin Compounds Containing Y,C,Y-Chelating Ligands359
16.2.1 Preparation of Organotin Compounds Containing Y,C,Y-Chelating Ligands L1Š5359
16.2.2 Structure, Dynamic Behaviour and Reactivity of Organotin Compounds Containing Y,C,Y-Chelating361
16.3 Organoaluminium, Antimony and Bismuth Compounds Containing Y,C,Y-Chelating Ligands L1Š4375
16.3.1 Synthesis of Organoaluminium(III) Derivatives375
16.3.2 Structure and Dynamic Behaviour of Organoaluminium(III) Compounds375
16.3.3 Reactivity of Organoaluminium(III) Derivatives376
16.3.4 Synthesis and Reactivity of Organoantimony(III) and Organobismuth(III) Derivatives377
16.3.5 Structure of Organoantimony(III) and Organobismuth(III) Derivatives378
Chapter 17 Stability of supported pincer complex-based catalysts in Heck catalysis385
17.1 Introduction385
17.2 Studies into the Stability of Pd-Pincer Complexes388
17.2.1 Stability of Pd-SCS Pincer Complexes390
17.2.2 Stability of Pd-PCP Pincer Complexes392
17.3 Conclusions395
Chapter 18 Dendrimers incorporating metallopincer functionalities: synthesis and applications399
18.1 Introduction399
18.2 Peripherally Substituted Systems402
18.2.1 Early Studies402
18.2.2 Dendrimers with NCN-Ni groups402
18.2.3 Dendritic Platinum and Palladium Pincers411
18.3 Metallopincers Within Each Dendrimer Generation420
18.3.1 Dendrimers Containing Pincer-Ligated Palladium and Platinum Complexes420
18.4 Focal Point and Core-Functionalized Metallopincer Dendrons and Dendrimers427
18.5 Conclusions and Future Perspectives431
Chapter 19 Perspective and prospects for pincer ligand chemistry441
Index445

Book details

Vendor Elsevier S & T
SKU 9780444531384
ISBN-13 9780080545158
Author Morales-Morales, David; Jensen, Craig G.M.
Category Science
Subject Organic

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Pincer complexes are formed by the binding of a chemical structure to a metal atom with at least one carbon-metal bond. Usually the metal atom has three bonds to a chemical backbone, enclosing the atom like a pincer. The resulting structure protects the metal atom and gives it unique properties.

The last decade has witnessed the continuous growth in the development of pincer complexes. These species have passed from being curiosity compounds to chemical chameleons able to perform a wide variety of applications. Their unique metal bound structures provide some of the most active catalysts yet known for organic transformations involving the activation of bonds. The Chemistry of Pincer Compounds details use of pincer compounds including homogeneous catalysis, enantioselective organic transformations, the activation of strong bonds, the biological importance of pincer compounds as potential therapeutic or pharmaceutical agents, dendrimeric and supported materials.

* Describes the chemistry and applications of this important class of organometallic and coordination compounds
* Covers the areas in which pincer complexes have had an impact
* Includes information on more recent and interesting pincer compounds not just those that are well-known

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