Catalysis without precious metals

Title:

Publication Information:

Weinheim : Wiley-VCH, 2010

Physical Description:

xviii, 290 p. : ill. ; 25 cm.

ISBN:

9783527323548

Subject Term:

Catalysis

Added Author:

Bullock, R. Morris

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Library	Item Barcode	Call Number	Material Type	Item Category 1	Status
Searching... PSZ JB	30000010249446	QD505 C38 2010	Open Access Book	Book	Searching... Unknown

Written for chemists in industry and academia, this ready reference and handbook summarizes recent progress in the development of new catalysts that do not require precious metals. The research thus presented points the way to how new catalysts may ultimately supplant the use of precious metals in some types of reactions, while highlighting the remaining challenges.
An essential copanion for organic and catalytic chemists, as well as those working with/on organometallics and graduate students.

From the contents:

* Catalysis Involving the H' Transfer Reactions of First-Row Transition Metals
* Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum Complexes
* Molybdenum and Tungsten Catalysts for Hydrogenation, Hydrosilylation and Hydrolysis
* Iron in Catalytic Alkene and Carbonyl Hydrogenation Reactions
* Olefin Oligomerizations and Polymerizations Catalyzed by Iron and Cobalt Complexes
* Cobalt and Nickel Catalyzed Reactions Involving C-H and C-N Activation Reactions
* Development of Molecular Electrocatalysts for H2 Oxidation and Production Based on Inexpensive Metals
* Nickel-Catalyzed Reductinve Couplings and Cyclizations
* Copper-Catalyzed Ligand Promoted Ullmann-Type Coupling Reactions
* Copper-Catalyzed Azide-Alkyne Cycloaddition
* "Frustrated Lewis Pairs": A Metal-Free Strategy for Hydrogenation Catalysis

Author Notes

After 21 years at Brookhaven National Laboratory in Long Island, New York, Morris Bullock moved to Pacific Northwest National Laboratory in 2006, where he is a Laboratory Fellow, as well as Director of the Center for Molecular Electrocatalysis. Dr. Bullock's research interests focus on reactivity of metal hydrides, including proton transfer, hydride transfer, and hydrogen atom transfer reactions, and on the development of molecular catalysts for the oxidation of hydrogen and production of hydrogen.

John Hartung and Jack R. NortonRichard R. SchrockR. Morris BullockPaul J. ChinkVernon C. Gibson and Gregory A. SolanRenee Becker and William D. JonesM. Rakowski DuBois and Daniel L. DuBoisHasnain A. Malik and Ryan D. Baxter and John MontgomeryYongwen Jiang and Dawei MaM.G. Finn and Valery V. FokinDouglas W. Stephan

Preface	p. XIII
List of Contributors	p. XVII
1 Catalysis Involving the H* Transfer Reactions of First-Row Transition Metals	p. 1
1.1 H* Transfer Between M-H Bonds and Organic Radicals	p. 2
1.2 H* Transfer Between Ligands and Organic Radicals	p. 4
1.3 H* Transfer Between M-H and C-C Bonds	p. 7
1.4 Chain Transfer Catalysis	p. 11
1.5 Catalysis of Radical Cydizations	p. 15
1.6 Competing Methods for the Cyclization of Dienes	p. 19
1.7 Summary and Conclusions	p. 20
References	p. 21
2 Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum	p. 25
2.1Introduction p. 25
2.2 Some Characteristics of Triamidoamine Complexes	p. 26
2.3 Possible [HIPTN 3 N]Mo Intermediates in a Catalytic Reduction of Molecular Nitrogen	p. 30
2.3.1 MoN 2 and MoN 2 -	p. 30
2.3.2 Mo-N=NH	p. 33
2.3.3 Conversion of Mo(N 2 ) into Mo-N=NH	p. 33
2.3.4 [Mo=N-NH 2 ] +	p. 35
2.3.5 Mo=N and [Mo=NH] +	p. 36
2.3.6 Mo(NH 3 ) and [Mo(NH 3 ) +	p. 37
2.4 Interconversion of Mo(NH 3 ) and Mo(N 2 )	p. 38
2.5 Catalytic Reduction of Dinitrogen	p. 39
2.6 MoH and Mo(H 2 )	p. 41
2.7 Ligand and Metal Variations	p. 44
2.8 Comments	p. 47
Acknowledgements	p. 48
References	p. 48
3 Molybdenum and Tungsten Catalysts for Hydrogenation, Hydrosilylation and Hydrolysis	p. 51
3.1 Introduction	p. 52
3.2 Proton Transfer Reactions of Metal Hydrides	p. 52
3.3 Hydride Transfer Reactions of Metal Hydrides	p. 54
3.4 Stoichiometric Hydride Transfer Reactivity of Anionic Metal Hydride Complexes	p. 56
3.5 Catalytic Hydrogenation of Ketones with Anionic Metal Hydrides	p. 58
3.6 Ionic Hydrogenation of Ketones Using Metal Hydrides and Added Acid	p. 59
3.7 Ionic Hydrogenations from Dihydrides: Delivery of the Proton and Hydride from One Metal	p. 64
3.8 Catalytic Ionic Hydrogenations With Mo and W Catalysts	p. 65
3.9 Mo Phosphine Catalysts With Improved lifetimes	p. 69
3.10 Tungsten Hydrogenation Catalysts with N-Heterocyclic Carbene Ligands	p. 70
3.11 Catalysts for Hydrosilylation of Ketones	p. 71
3.12 Cp 2 Mo Catalysts for Hydrolysis, Hydrogenations and Hydrations	p. 73
3.13 Conclusion	p. 78
Acknowledgements	p. 78
References	p. 79
4 Modern Alchemy: Replacing Precious Metals with Iron in Catalytic Alkene and Carbonyl Hydrogenation Reactions	p. 83
4.1 Introduction	p. 83
4.2 Alkene Hydrogenation	p. 86
4.2.1 Iron Carbonyl Complexes	p. 86
4.2.2 Iron Phosphine Compounds	p. 89
4.2.3 Bis(imino)pyridine Iron Complexes	p. 93
4.2.4 ¿-Diimine Iron Complexes	p. 99
4.3 Carbonyl Hydrogenation	p. 101
4.3.1 Hydrosilylation	p. 101
4.3.2 Bifunctional Complexes	p. 103
4.4 Outlook	p. 205
References	p. 206
5 Olefin Oligomerizations and Polymerizations Catalyzed by Iron and Cobalt Complexes Bearing Bis(imino)pyridine Ligands	p. 222
5.1 Introduction	p. 122
5.2 Precatalyst Synthesis	p. 222
5.2.1 Ligand Preparation	p. 112
5.2.2 Complexation with MX 2 (M = Fe, Co)	p. 113
5.3 Precatalyst Activation and Catalysis	p. 115
5.3.1 Olefin Polymerization	p. 115
5.3.1.1 Catalytic Evaluation	p. 116
5.3.1.2 Steric Versus Electronic Effects	p. 116
5.3.1.3 Effect of MAO Concentration	p. 119
5.3.1.4 Effects of Pressure and Temperature	p. 120
5.3.1.5 ¿-Olefin Monomers	p. 121
5.3.2 Olefin Oligomerization	p. 122
5.3.2.1 Catalytic Evaluation	p. 122
5.3.2.2 Substituent Effects	p. 122
5.3.2.3 Schulz-Flory Distributions	p. 124
5.3.2.4 Poisson Distributions	p. 124
5.3.2.5 ¿-Olefin Monomers	p. 125
5.4 The Active Catalyst and Mechanism	p. 125
5.4. Active Species	p. 225
5.4.1.1 Iron Catalyst	p. 126
5.4.1.2 Cobalt Catalyst	p. 127
5.4.2 Propagation and Chain Transfer Pathways/Theoretical Studies	p. 127
5.4.3 Well-Defined Iron and Cobalt Alkyls	p. 129
5.5 Other Applications	p. 133
5.5.1 Immobilization	p. 133
5.5.2 Reactor Blending and Tandem Catalysis	p. 134
5.6 Conclusions and Outlook	p. 134
References	p. 136
6 Cobalt and Nickel Catalyzed Reactions Involving C-H and C-N Activation Reactions	p. 143 "
6.1 Introduction	p. 143
6.2 Catalysis with Cobal	p. 143
6.3 Catalysis with Nickel	p. 154
References	p. 163
7 A Modular Approach to the Development of Molecular Electrocatalysts for H 2 Oxidation and Production Based on Inexpensive Metals	p. 265
7.1 Introduction	p. 265
7.2 Concepts in Catalyst Design Based on Structural Studies of Hydrogenase Enzymes	p. 266
7.3 A Layered or Modular Approach to Catalyst Design	p. 270
7.4 Using the First Coordination Sphere to Control the Energies of Catalytic Intermediates	p. 272
7.5 Using the Second Coordination Sphere to Control the Movement of Protons between the Metal and the Exterior of the Molecular Catalyst	p. 173
7.6 Integration of the First and Second Coordination Spheres	p. 174
7.7 Summary	p. 178
Acknowledgements	p. 179
References	p. 179
8 Nickel-Catalyzed Reductive Couplings and Cyclizations	p. 182
8.1 Introduction	p. 182
8.2 Couplings of Alkynes with ¿,ß-Unsaturated Carbonyls	p. 182
8.2.1 Three-Component Couplings via Alkyl Group Transfer-Methods Development	p. 182
8.2.2 Reductive Couplings via Hydrogen Atom Transfer-Methods Development	p. 184
8.2.3 Mechanistic Insights	p. 186
8.2.3.1 Metallacycle-Based Mechanistic Pathway	p. 186
8.2.4 Use in Natural Product Synthesis	p. 189
8.3 Couplings of Alkynes with Aldehydes	p. 192
8.3.1 Three-Component Couplings via Alkyl Group Transfer-Method Development	p. 192
8.3.2 Reductive Couplings via Hydrogen Atom Transfer-Method Development	p. 193
8.3.2.1 Simple Aldehyde and Alkyne Reductive Couplings	p. 194
8.3.2.2 Directed Processes	p. 196
8.3.2.3 Diastereoselective Variants: Transfer of Chirality	p. 197
8.3.2.4 Asymmetric Variants	p. 199
8.3.3 Mechanistic Insights	p. 200
8.3.4 Cydocondensations via Hydrogen Gas Extrusion	p. 204
8.3.5 Use in Natural Product Synthesis	p. 205
8.4 Conclusions and Outlook	p. 220
Acknowledgements	p. 220
References	p. 220
9 Copper-Catalyzed Ligand Promoted Ullmann-type Coupling Reactions	p. 213
9.1 Introduction	p. 213
9.2 C-N Bond Formation	p. 213
9.2.1 Arylation of Amines	p. 213
9.2.1.1 Arylation of Aliphatic Primary and Secondary Amines	p. 213
9.2.1.2 Arylation of Aryl Amines	p. 215
9.2.1.3 Arylation of Ammonia	p. 215
9.2.2 Arylation and Vinylation of N-Heterocycles	p. 227
9.2.2.1 Coupling of Aryl Halides and N-Heterocycles	p. 217
9.2.2.2 Coupling of Vinyl Bromides and N-Heterocycles	p. 218
9.2.3 Aromatic Amidation	p. 218
9.2.3.1 Cross-Coupling of aryl Halides with Amides and Carbamates	p. 219
9.2.3.2 Cross-Coupling of Vinyl Halides with Amides or Carbamates	p. 220
9.2.3.3 Cross-Coupling of Alkynl Halides with Amides or Carbamates	p. 220
9.2.4 Azidation	p. 221
19.3 C-0 Bond Formation	p. 222
9.3.1 Synthesis of Diaryl Ethers	p. 222
9.3.2 Aryloxylation of Vinyl Halides	p. 223
9.3.3 Cross-Coupling of Aryl Halides with Aliphatic Alcohols	p. 223
9.4 C-C Bond Formation	p. 224
9.4.1 Cross-Coupling with Terminal Acetylene	p. 224
9.4.2 The Arylation of Activated Methylene Compounds	p. 225
9.4.3 Cyanation	p. 227
9.5 C-S Bond Formation	p. 228
9.5.1 The Formation of Bisaryl- and Arylalkyl-Thioethers	p. 228
9.5.2 The Synthesis of Alkenylsulfides	p. 229
9.5.3 Assembly of aryl Sulfones	p. 229
9.6 C-P Bond Formation	p. 230
9.7 Conclusion	p. 230
References	p. 231
10 Copper-Catalyzed Azide-Alkyne Cycloaddition (CuAAC)	p. 235
10.1 Introduction	p. 235
10.2 Azide-Alkyne Cycloaddition: Basics	p. 237
10.3 Copper-Catalyzed Cycloadditions	p. 238
10.3.1 Catalysts and Ligands	p. 238
10.3.2 CuAAC with In Situ Generated Azides	p. 244
10.3.3 Mechanistic Aspects of the CuAAC	p. 244
10.3.4 Reactions of Sulfonyl Azides	p. 250
10.3.5 Copper-Catalyzed Reactions with Other Dipolar Species	p. 251
10.3.6 Examples of Application of the CuAAC Reaction	p. 252
10.3.6.1 Synthesis of Compound libraries for Biological Screening	p. 252
10.3.6.2 Copper-Binding Adhesives	p. 253
10.3.7 Representative Experimental Procedures	p. 255
Acknowledgements	p. 256
References	p. 257
11 "Frustrated Lewis Pairs": A Metal-Free Strategy for Hydrogenation Catalysis	p. 261
11.1 Phosphine-Borane Activation of H 2	p. 263
11.2 "Frustrated Lewis Pairs"	p. 264
11.3 Metal-Free Catalytic Hydxogenation	p. 267
11.4 Future Considerations	p. 273
Acknowledgements	p. 273
References	p. 273
Index	p. 277

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