Giambastiani / Campora Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes I

State-of-the-art and Perspectives
1. Auflage 2011
ISBN: 978-90-481-3815-9
Verlag: Springer-Verlag
Format: PDF
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)

E-Book, Englisch, 288 Seiten

This book highlights key advances that have occurred in the field of olefin conversion in recent years. The role of homogenous transition metal catalysts which contain an imine functionality is emphasized; their potential applications in the processing and upgrade of olefins to a wide variety of commodity products of very high industrial value is also explored. On the threshold of the fiftieth anniversary of the Noble Prize to Ziegler and Natta, this book gives a critical summary of the state of the art developments in the fascinating and rapidly developing field of the olefin polymerization, oligomerization, and co-polymerization catalysis.

Autoren/Hrsg.

Giambastiani, Giuliano

Campora, Juan

Inhaltsverzeichnis

1;Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes I;4
2;1 Cr Complexes of Nitrogen Donor Ligands for Olefin Oligomerisation and Polymerisation;12
2.1;Abstract;12
2.2;1.1…Introduction;12
2.3;1.2…Cr Complexes of Cyclopentadienyl Ligands Containing Pendant N-donors;13
2.4;1.3…Chromium Complexes of beta -diketiminate (NacNac) and beta -ketoiminate (NacAc) Type Ligands;16
2.5;1.4…Chromium Complexes of Imidazole and Pyrazole Based Ligands;18
2.6;1.5…Chromium Complexes of Bis(imino)pyridine and Structurally Related Ligands;19
2.7;1.6…Chromium Complexes of Other N-donor Ligands;21
2.8;1.7…Selective Oligomerisation via Metallacycle Intermediates;22
2.8.1;1.7.1 The Phillips Trimerisation Catalyst;23
2.8.2;1.7.2 Trimerisation Catalysts Based on Chromium Complexes of Tridentate Ligands;24
2.8.3;1.7.3 Chromium Complexes of Bidentate Ligands;29
2.8.4;1.7.4 Oligomerisation and Polymerisation via Extended Metallacycles;30
2.9;1.8…Summary and Outlook;31
2.10;References;32
3;2 Late-Transition Metal Complexes with Mixed NO, NS, NP Chelating Ligands for Olefin Polymerization Catalysis;38
3.1;Abstract;38
3.2;2.1…Introduction;38
3.3;2.2…Mixed Ligand Concept;40
3.3.1;2.2.1 N--O Ligands;41
3.3.2;2.2.2 N--P and N--S Ligands;46
3.4;2.3…Group X Metal Complexes;49
3.5;2.4…Application in Homogeneous Catalyzed Polymerization;51
3.5.1;2.4.1 Activation;51
3.5.2;2.4.2 Ethylene Polymerization;75
3.5.3;2.4.3 Copolymerization of Ethylene with Monomers with Functional Groups;101
3.5.4;2.4.4 Aqueous Olefin Polymerization;109
3.6;2.5…Mechanistic Aspects;112
3.6.1;2.5.1 Mechanism of Ethylene Homopolymerization;112
3.6.2;2.5.2 Mechanism of Copolymerization of Ethylene with Polar Monomers;117
3.7;2.6…Summary and Conclusions;119
3.8;Acknowledgments;122
3.9;References;122
4;3 Rare-Earth Metal Complexes Supported by Nitrogen-Containing Ligands in Olefin Polymerization;130
4.1;Abstract;130
4.2;3.1…Introduction;130
4.3;3.2…Ethylene Polymerization;136
4.3.1;3.2.1 Neutral Alkyl Rare-Earth Metal Complexes;136
4.3.2;3.2.2 Cationic Alkyl Rare-Earth Metal Complexes;137
4.3.3;3.2.3 Cationic Alkyl Rare-Earth Metal Complexes Supported by N2-Ligands;137
4.3.4;3.2.4 Cationic Alkyl Rare-Earth Metal Complexes Supported by N3-Ligands;147
4.3.5;3.2.5 Cationic Alkyl Rare-Earth Metal Complexes Supported by N4-Ligands;147
4.3.6;3.2.6 Cationic Alkyl Rare-Earth Metal Complexes Supported by N5-Ligands;149
4.3.7;3.2.7 Cationic Alkyl Rare-Earth Metal Complexes Supported by N6-Ligands;149
4.3.8;3.2.8 Cationic Alkyl Complexes Supported by N,O-Ligands;150
4.4;3.3…Hydrido Rare-Earth Metal Complexes Supported by Nitrogen-Containing Ligands;150
4.5;3.4… alpha -Olefin Polymerization;152
4.5.1;3.4.1 Cationic Alkyl Complexes;152
4.5.2;3.4.2 Hydrido Complexes;155
4.6;3.5…Styrene Polymerization;155
4.7;3.6…Outlook;159
4.8;References;159
5;4 Imine-Based Vanadium Catalysts for alpha -Olefin Polymerization;164
5.1;Abstract;164
5.2;4.1…Introduction;165
5.3;4.2…N,N--Bi-Dentate Ligands;166
5.3.1;4.2.1 alpha -Diimines;166
5.3.2;4.2.2 Iminopyrrolide;167
5.3.3;4.2.3 beta -Diiminate/Amidinate;168
5.4;4.3…N,N,N-Tri-Dentate Ligands;171
5.4.1;4.3.1 Bis(imino)pyridines;171
5.4.2;4.3.2 2,6-Bis(aryliminophosphoranyl)pyridine;178
5.4.3;4.3.3 Bis(pyrazolyl)pyridine;179
5.4.4;4.3.4 Bis(benzimidazole)amine;179
5.5;4.4…N,O--Bi-Dentate Ligands;180
5.5.1;4.4.1 Salicylaldiminato/Phenoxyimines;180
5.5.1.1;4.4.1.1 Bi-Dentate;180
5.5.1.1.1;Imidazolium Bearing Phenoxyimines;183
5.5.1.1.2;Imido Phenoxyimines;183
5.5.1.1.3;‘C-capped’ Phenoxyimines;184
5.5.1.2;4.4.1.2 Tri-Dentate Salicylaldiminato/Phenoxyimines;188
5.5.1.3;4.4.1.3 Tetra-Dentate Salicylaldiminato/Phenoxyimines;189
5.5.2;4.4.2 beta -Enaminoketonato;192
5.5.3;4.4.3 Pyridine Alkoxide;194
5.6;4.5…N,O,S-Penta-/Hexa-Dentate Salicylaldiminato/Phenoxyimines;194
5.7;4.6…Other;195
5.7.1;4.6.1 Ketimide;195
5.7.2;4.6.2 Tris(3,5-dimethylpyrazolyl)borato (Tp*);196
5.7.3;4.6.3 Phthalocyanine;199
5.7.4;4.6.4 (2-Anilidomethyl)pyridine;199
5.7.5;4.6.5 Quinolinolato;201
5.7.6;4.6.6 Lutidene;201
5.8;4.7…Concluding Remarks;202
5.9;Acknowledgments;202
5.10;References;202
6;5 Imino- and Amido-Pyridinate d-Block Metal Complexes in Polymerization/Oligomerization Catalysis;207
6.1;Abstract;207
6.2;5.1…Introduction;209
6.3;5.2…Synthesis of Iminopyridyl Ligands;210
6.4;5.3…Synthesis of Iminopyridyl-Based Late Transition Metal Complexes;212
6.4.1;5.3.1 FeII-(imino)pyridinate Complexes;213
6.4.2;5.3.2 CoII-(imino)pyridinate Complexes;213
6.4.3;5.3.3 NiII- and PdII-(imino)pyridinate Complexes;215
6.5;5.4…Principal Activators and Mechanistic Considerations;219
6.5.1;5.4.1 Olefin Polymerization by 8--10 Group Metal (imino)pyridyl-Based Catalysts;226
6.5.2;5.4.2 Olefin Oligomerization by Group 8--10 Metal (imino)pyridinato Catalysts;228
6.5.3;5.4.3 NiII and CoII-iminopyridine Systems in Tandem Co-polymerization Catalysis;234
6.5.4;5.4.4 Atom Transfer Radical Polymerization by CuI and FeII Iminopyridinate Catalysts;237
6.6;5.5…Synthesis of Group(IV) Metal Amidoalkylpyridinate Complexes;238
6.6.1;5.5.1 Olefin Polymerization Behavior of Group(IV) Metal Amidoalkylpyridinate Complexes;242
6.7;5.6…Synthesis of 6-Aryl(heteroaryl)-substituted Aminoalkylpyridyl Ligands;244
6.7.1;5.6.1 Synthesis of 6-Aryl(heteroaryl)-substituted Amidoalkylpyridinato Group IV Metal Complexes;248
6.8;5.7…Olefin Polymerization Using 6-Aryl(heteroaryl)-substituted Amidoalkylpyridinato Group IV Metal Complexes;254
6.8.1;5.7.1 Polymerization of Propylene;256
6.8.2;5.7.2 Ethylene/ alpha -Olefin Copolymerization;260
6.8.3;5.7.3 Chain Shuttling Polymerization;261
6.8.4;5.7.4 Olefin Polymerization Mechanism;265
6.8.5;5.7.5 6-Aryl(heteroaryl)-substituted Amidoalkylpyridinato Yttrium Complexes;270
6.8.6;5.7.6 6-Aryl(heteroaryl)-substituted Aminoalkylpyridinato Chromium Complexes;272
6.9;5.8…Aminopyridyl Ligands and Related Group III--IV Metal Complexes;277
6.9.1;5.8.1 Synthesis of 6-Aryl-Aminopyridyl Ligands;277
6.9.2;5.8.2 Synthesis of 6-Aryl-Amidopyridinato Complexes;277
6.9.2.1;5.8.2.1 Group III and Rare Earth Metal Complexes;277
6.9.2.2;5.8.2.2 Group IV Metal Complexes;279
6.9.3;5.8.3 Polymerization Activity of 6-Aryl-substituted Amidopyridyl (Ap) Complexes;282
6.9.3.1;5.8.3.1 Polymerization by Group III and Rare Earth Metal Complexes;282
6.9.3.2;5.8.3.2 Polymerization by Group IV Metal Complexes;283
6.10;5.9…Conclusions;285
6.11;References;285
7;Subject Index;292
8;Foreword;6
9;Preface;7
10;Contents;9
11;List of Contributors;10