Catalysis Books

Book SynopsisDiscover the latest research in photocatalysis combined with foundational topics in basic physical and chemical photocatalytic processes In Heterogeneous Photocatalysis: From Fundamentals to Applications in Energy Conversion and Depollution, distinguished researcher and editor Jennifer Strunk delivers a rigorous discussion of the two main topics in her field—energy conversion and depollution reactions. The book covers topics like water splitting, CO2 reduction, NOx abatement and harmful organics degradation. In addition to the latest research on these topics, the reference provides readers with fundamental information about elementary physical and chemical processes in photocatalysis that are extremely practical in this interdisciplinary field. It offers an excellent overview of modern heterogeneous photocatalysis and combines concepts from different viewpoints to allow researchers with backgrounds as varied as electrochemistry, material science, and semiconductor physics to begin developing solutions with photocatalysis. In addition to subjects like metal-free photocatalysts and photocarrier loss pathways in metal oxide absorber materials for photocatalysis explored with time-resolved spectroscopy, readers will also benefit from the inclusion of: Thorough introductions to kinetic and thermodynamic considerations for photocatalyst design and the logic, concepts, and methods of the design of reliable studies on photocatalysis Detailed explorations of in-situ spectroscopy for mechanistic studies in semiconductor photocatalysis and the principles and limitations of photoelectrochemical fuel generation Discussions of photocatalysis, including the heterogeneous catalysis perspective and insights into photocatalysis from computational chemistry Treatments of selected aspects of photoreactor engineering and defects in photocatalysis Perfect for photochemists, physical and catalytic chemists, electrochemists, and materials scientists, Heterogeneous Photocatalysis will also earn a place in the libraries of surface physicists and environmental chemists seeking up-to-date information about energy conversion and depollution reactions.Table of ContentsKinetic and Thermodynamic Considerations for Photocatalyst Design Design of Reliable Studies on Photocatalysis: Logic, Concepts and Methods In-Situ Spectroscopy for Mechanistic Studies in Semiconductor Photocatalysis Principles and Limitations of Photoelectrochemical Fuel Generation Photocatalysis - The Heterogeneous Catalysis Perspective Insights into Photocatalysis from Computational Chemistry Selected Aspects of Photoreactor Engineering Defects in photocatalysis Photocarrier Loss Pathways in Metal Oxide Absorber Materials for Photocatalysis Explored with Time-Resolved Spectroscopy: The Case of BiVO4 Metal-Free Photocatalysts Photocatalytic water splitting: Fundamentals and current concepts Photocatalytic CO2 reduction and beyond Photocatalytic NOx Abatement Photoactive Nanomaterials: Applications in Wastewater Treatment and their Environmental Fate

Read more less

Book SynopsisStudies of free radicals on surfaces are of interest for several reasons: the spontaneous or stimulated formation of radicals from adsorbed molecules may represent one possible mechanism for heterogeneous catalysis. In some cases the radicals are ionic, indicating that primary oxidation and reduction reactions occur. Radicals can also be used as probes to investigate diffusion processes on catalytic surfaces. The first direct observations were made more than 30 years ago, but detailed studies of structure, reactions and mobility have only recently become feasible with the advent of powerful spectroscopic techniques, to a great extent developed and used by the contributors to this volume. This comprehensive review describes new trends in the field. Leading experts write about the nature of surface active sites, methods to identify them, and the radicals formed from adsorbed molecules interacting with the surface. The emphasis is on the fundamentals covering thermal, photostimulated and radiation induced reactions as well as diffusion processes. This provides the necessary background for technological applications. This book will be useful to those who are interested in surface chemistry, heterogeneous catalysis as well as those who want to study reactive intermediates in chemical reactions. It is also of interest to scientists in photo and radiation physics and chemistry. Table of ContentsI: Properties of Catalytic Surfaces 1.- 1.1 EPR Characterization of Oxide Supported Transition Metal Ions: Relevance to Catalysis.- 1.2 Study of Catalytic Site Structure and Diffusion of Radicals in Porous Heterogeneous Systems with ESR, ENDOR and ESE.- 1.3 Theoretical Studies of Core Ionization, Excitation and De-excitation of Adsorbates.- II: Structure and Reactivity of Radicals on Surfaces 87.- II. 1 Electron Magnetic Resonance of Aromatic Radicals on Metal Oxide Surfaces 89.- II.2 ESR Studies of Organic Radical Cations in Zeolites.- II.3 Surface Trapped Electrons on Metal Vapour Modified Magnesium Oxide. Nature of Surface Centres and Reactivity with Adsorbed Molecules.- II.4 Radicals on Surfaces Formed by Ionizing Radiation.- II.5 Photostimulated Formation of Radicals on Oxide Surfaces.- III: Trends in Modern Techniques 227.- III. 1 Fourier Transform Electron Paramagnetic Resonance Studies of Photochemical Reactions in Heterogeneous Media.- III.2 Muon Spin Resonance of Radicals on Surfaces.- III.3 Investigation of Radical Ions with Time-Resolved Surface Enhanced Raman Spectroscopy.

Read more less

Book SynopsisVolume 5 in the Catalysts for Fine Chemical Synthesis series describes new procedures for the regio- and stereo-controlled transformations of compounds involving oxidation or reduction reactions. It describes a wide range of catalysts, including organometallic systems, biocatalysts and biomimetics.Table of ContentsCHAPTER 1: Industrial Catalysts for Regio- or Stereo- selective Oxidations and Reductions. A Review of Key Technologies and Targets. J. Whittall CHAPTER 2: Asymmetric Hydrogenation of Alkenes, Enones, Ene-esters and Ene-Acids 2.1: (S)-2,2'- Bis{[di(4-methoxyphenyl)phosphinyl]oxy}-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation I. Gergely, C. Hegeds and J. Bakos. 2.2: Synthesis and Application of Phosphinite Oxazoline Iridium Complexes for the Asymmetric Hydrogenation of Alkenes F. Menges and A. Pfaltz. 2.3: Synthesis and Application of Heterocyclic Phosphine Oxazoline (HetPHOX) Iridium Complexes for the Asymmetric Hydrogenation of Alkenes F. Menges and P.G. Cozzi. 2.4: (R)-2,2',6,6'- Tetramethoxy-bis[di(3,5-dimethylphenyl)phosphino]-3,3'-bipyridine [(R)-Xyl-P-Phos] as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation of a-Dehydroamino Acids J. Wu and A.S.C. Chan. 2.5: (R,R)-2,3-Bis(tert-butylmethylphosphine)quinoxaline (Quinox P*) as a Ligand for Rhodium-Catalysed Asymmetric Hydrogenation of Prochiral Amino Acid and Amine Derivatives T. Imamoto and A. Koide. 2.6: Rhodium-Catalysed Asymmetric Hydrogenation of Indoles R. Kuwano and M. Sawamura. CHAPTER 3: Asymmetric Reduction of Ketones 3.1: (R,R)-Bis(diphenylphosphino)-1,3-diphenylpropane as a Versatile Ligand for Enantioselective Hydrogenations N. Dubrovina and A. Borner. 3.2: Synthesis of Both Enantiomers of 1-Phenylethanol by Reduction of Acetophenone with Geotrichum candidum IFO 5767 K. Nakamura, M. Fujii and Y. Ida. 3.3: Titanocene-Catalysed Reduction of Ketones in the Presence of Water. A Convenient Procedure for the Synthesis of Alcohols by Free-Radical Chemistry A. Rosales, J.M. Cuerva and J.E. Oltra. 3.4: Xyl-TetraPHEMP: A Highly Efficient Biaryl Ligand in the [Diphosphine RuCl2-diamine]-Catalysed Hydrogenation of Simple Aromatic Ketones P.H. Moran, J.P. Henschke, A. Zanotti-Gerosa and I C. Lennon. 3.5: N-Arenesulfonyl- and N-Alkylsulfamoyl-1,2-diphenylethylenediamine Ligands for Ruthenium-Catalysed Asymmetric Transfer Hydrogenation of Activated Ketones M.S. Stephan and B. Mohar. 3.6: The Synthesis and Application of BrXUPHOS: A Novel Monodentate Phosphorus Ligand for the Asymmetric Hydrogenation of Ketones M. Wills, Y. Xu, G. Docherty and G. Woodward. 3.7: In Situ Formation of Ligand and Catalyst: Application in Ruthenium-Catalysed Enantioselective Reduction of Ketones J. Wettergren and H. Adolfsson. 3.8: SYNPHOS and DIFLUORPHOS as Ligands for Ruthenium-Catalysed Hydrogenation of Alkenes and Ketones S. Jeulin, V. Ratovelomanana-Vidal and J-P. Genet. 3.9: An Arene Ruthenium Complex with Polymerizable Side-chains for the Synthesis of Immobilised Catalysts E. Burri, S.B. Wendicke, K. Severin. 3.10: Selective Reduction of Carbonyl Group in beta, gamma- Unsaturated alpha- Ketoesters by Transfer Hydrogenation with Ru-(para-cymene) (TsDPEN) M. Guo, D. Li, Y. Sun and Z. Zhang. 3.11: Preparation of Polymer-Supported Ru-TsDPEN Catalysts and their Use for the Enantioselective Synthesis of (S)-Fluoxetine L. Chai, Y. Li and Q. Wang. 3.12: Polymer-Supported Chiral Sulfonamide-Catalysed Reduction of B-Keto Nitrile: a Practical Synthesis of (R)-Fluoxetine G.Wang and G. Zhao. CHAPTER 4: Imine Reduction and Reductive Amination 4.1: Metal-Free Reduction of Imines: Enantioselective Bronsted Acid-Catalysed Transfer Hydrogenation using Chiral BINOL-Phosphates as Catalysts M. Rueping, E. Sugiono, C. Azap and T. Theissmann. 4.2: Metal-Free Bronsted Acid-Catalysed Transfer Hydrogenation: Enantioselective Synthesis of Tetrahydroquinolines M. Rueping , T. Theissmann and A. P. Antonchick. 4.3: A Highly Stereoselective Synthesis of 3a-Amino-23,24-bisnor-5a-cholane via Reductive Amination S. N. Khan, N.J. Cho and H-S. Kim. CHAPTER 5: Oxidation of Primary and Secondary Alcohols 5.1: Copper (II)-Catalysed Oxidation of Primary Alcohols to Aldehydes with Atmospheric Oxygen S. Jammi and T. Punniyamurthy. 5.2: Solvent-free Dehydrogenation of Secondary Alcohols in the Absence of Hydrogen Abstractors using Robinson's Catalyst G.B.W.L. Ligthart, R.H. Meijer, J. v. Buijtenen, J. Meuldijk, J.A.J.M. Vekemans and L. A. Hulshof. 5.3: 2-Iodoxybenzoic Acid (IBX)/ n-Bu4NBr/ CH2Cl2-H2O: a Mild System for the Selective Oxidation of Secondary Alcohols K. Kittigowittana, M. Pohmakotr, V. Reutrakul and C. Kuhakarn. CHAPTER 6: Hydroxylation, Epoxidation and Related Reactions 6.1: Proline-Catalysed a-Aminoxylation of Aldehydes and Ketones Y. Hayashi and M. Shoji. 6.2: Ru/ Silica* Cat* TEMPO(c)-Mediated Oxidation of Alkenes to a-Hydroxyacids R. Ciriminna and M. Pagliaro. 6.3: Catalytic Enantioselective Epoxidation of trans-Disubstituted and Trisubstituted Alkenes with Arabinose-Derived Ulose T.K. M. Shing, G.Y.C. Leung and T. Luk. 6.4: VO(acac)2/ TBHP-Catalysed Epoxidation of 2-(2-Alkenyl)phenols. Highly Regio- and Diastereo-selective Oxidative Cyclisation to 2,3-Dihydrobenzofuranols and 3-Chromanols A. Lattanzi and A. Scettri. 6.5: An Oxalolidinone Ketone Catalyst for the Asymmetric Epoxidation of cis-Olefins D. Goeddel and Y. Shi. 6.6: a-Fluorotropinone Immobilised on Silica: a New Stereoselective Heterogeneous Catalyst for Epoxidation of Alkenes with Oxone G. Sartori, A. Armstrong, R. Maggi, A. Mazzacani, R. Sartorio, F. Bigi and B. Dominguez-Fernandez. 6.7: Asymmetric Epoxidation Catalysed by Novel Azacrown Ether-Type Chiral Quaternary Ammonium Salts under Phase-Transfer Catalytic Conditions K. Hori, K. Tani, and Y. Tohda. 6.8: Enantioselective Epoxidation of Olefins using Phase-Transfer Conditions and [6-N-((S)-1,2,2-Trimethylpropyl)-5H-dibenz[c,e]azepinium] [rac-TRISPHAT] Salt as Catalyst J. Vachon, C. Perollier, A. Martinez and J. Lacour. 6.9: Catalytic Asymmetric Epoxidation of a,Unsaturated Esters Promoted by a Yttrium-Biphenyldiol Complex M. Shibasaki, H. Kakei and S. Matsunaga.. 6.10: Catalytic Enantioselective Epoxidation of a, -Enones with a BINOL-Zinc Complex A. Minatti and K.H. Dotz 6.11: Asymmetric Epoxidation of Phenyl 2-(3'-Pyridylvinyl) Sulfone using Polyleucine/ Hydrogen Peroxide Gel M. Pitts and J. Whittall. CHAPTER 7: Oxidation of Ketones to Lactones or Enones 7.1: Synthesis of 2-(Phosphinophenyl)pyridine Ligand and its Application to Palladium-Catalysed Asymmetric Baeyer- Villiger Oxidation of Prochiral Cyclobutanones K. Ito and T. Katsuki. 7.2: (D)-Codeinone from (D)-Dihydrocodeinone via the Use of Modified o-Iodoxybenzoic Acid (IBX) P. Mather and J. Whittall. CHAPTER 8: Oxidative C-C Coupling 8.1: Enantioselective Oxidative Coupling of 2-Naphthols Catalysed by a Novel Chiral Vanadium Complex N-S. Xie, Q-Z. Liu, Z-B. Luo, L-Z. Gong, A-Q. Mi and Y-Z. Jiang. 8.2: Catalytic Oxidative Cross-Coupling Reaction of 2-Naphthol Derivatives S. Habaue and T. Temma. 8.3: Oxidative Coupling of Benzene with a,-Unsaturated Aldehydes by Pd(OAc)2/ HPMoV/ O2 System T. Yamada, S. Sakaguchi and Y. Ishii. CHAPTER 9: Oxidation of Sulfides and Sulfoxides 9.1: The First Example of Direct Oxidation of Sulfides to Sulfones by an Osmate- Molecular Oxygen System B.M. Choudary, C. Reddy, V. Reddy, B.V. Prakash, M.L. Kantam and B. Sreedhar. 9.2: Selective Oxidation of Sulfides to Sulfoxides and Sulfones using Hydrogen Peroxide (H2O2) in the Presence of Zirconium Tetrachloride K. Bahrami. 9.3: WO3-30% H2O2-Cinchona Alkaloids: a New Heterogeneous Catalytic System for Asymmetric Oxidation and Kinetic Resolution of Racemic Sulfoxides V. V. Thakur and A. Sudalai. 9.4: Benzyl-4,6-isopropylidene-a-(D)-glucopyranoside, 2-deoxy-2-[[(2-hydroxy-3,5-di-tert-butylphenyl)methylene]amine] as a Ligand for Vanadium-Catalysed Asymmetric Oxidation of Sulfides R. Del Litto, G. Roviello and F. Ruffo. 9.5: Asymmetric Sulfoxidation of Aryl Methyl Sulfides with H2O2 in Water A. Scarso and G. Strukul

Read more less

Book SynopsisOver the last 60 years the increasing knowledge of transition metal chemistry has resulted in an enormous advance of homogeneous catalysis as an essential tool in both academic and industrial fields. Remarkably, phosphorus(III) donor ligands have played an important role in several of the acknowledged catalytic reactions. The positive effects of phosphine ligands in transition metal homogeneous catalysis have contributed largely to the evolution of the field into an indispensable tool in organic synthesis and the industrial production of chemicals. This book aims to address the design and synthesis of a comprehensive compilation of P(III) ligands for homogeneous catalysis. It not only focuses on the well-known traditional ligands that have been explored by catalysis researchers, but also includes promising ligand types that have traditionally been ignored mainly because of their challenging synthesis. Topics covered include ligand effects in homogeneous catalysTable of ContentsList of Contributors xv Preface xix 1 Phosphorus Ligand Effects in Homogeneous Catalysis and Rational Catalyst Design 1 Jason A. Gillespie, Erik Zuidema, Piet W. N. M. van Leeuwen, and Paul C. J. Kamer 1.1 Introduction 1 1.2 Properties of phosphorus ligands 7 1.2.1 Electronic ligand parameters 7 1.2.2 Steric ligand parameters 9 1.2.3 Bite angle effects 10 1.2.3.1 Electronic bite angle effect 11 1.2.3.2 Steric bite angle effect 12 1.2.3.3 Steric versus electronic bite angle effects 12 1.2.4 Molecular electrostatic potential (MESP) approach 13 1.3 Asymmetric ligands 15 1.4 Rational ligand design in nickel-catalysed hydrocyanation 19 1.4.1 Introduction 19 1.4.2 Mechanistic insights 20 1.4.3 Rational design 20 1.5 Conclusions 22 References 23 2 Chiral Phosphines and Diphosphines 27 Wei Li and Xumu Zhang 2.1 Introduction 27 2.1.1 Early developments 27 2.2 Chiral chelating diphosphines with a linking scaffold 30 2.2.1 Building chiral backbones from naturally available materials 30 2.2.1.1 Early development 30 2.2.1.2 Syntheses of DIOP variants 31 2.2.1.3 Synthesis from other natural chiral backbones 33 2.2.2 Design and synthesis of chiral backbones 35 2.2.2.1 Chiral backbones synthesized through asymmetric catalysis 35 2.2.2.2 Design and synthesis of ligands containing spiro backbones 37 2.2.2.3 Design and synthesis of chiral ferrocene backbones 40 2.2.2.4 Design and synthesis of other chiral backbones 41 2.2.3 Synthesis from optical resolution of phosphine precursors or intermediates 43 2.3 Chiral atropisomeric biaryl diphosphines 46 2.3.1 Synthesis of BINAP and its derivatives 46 2.3.2 Synthesis of atropisomeric biaryl ligands 49 2.3.3 General strategies of synthesizing of atropisomeric biaryl ligands 52 2.4 Chiral phosphacyclic diphosphines 52 2.4.1 Fundamental discovery and syntheses of BPE and DuPhos 52 2.4.2 Design and synthesis of bisphosphetanes 56 2.4.3 Design and synthesis of bisphospholanes 58 2.4.3.1 BPE and DuPhos analogue ligands 58 2.4.3.2 P-stereogenic bisphospholane ligands 60 2.4.4 Design and synthesis of bisphospholes 63 2.4.5 Design and synthesis of bisphosphinanes 65 2.4.6 Design and synthesis of bisphosphepines 66 2.4.7 Summary of synthetic strategies of phosphacycles 68 2.5 P-stereogenic diphosphine ligands 68 2.6 Experimental procedures for the syntheses of selected diphosphine ligands 69 2.6.1 Synthesis procedure for DIOP* ligand 69 2.6.2 Synthesis procedure of SDP ligands 70 2.6.3 Synthesis procedure of ( R , R )-BICP 71 2.6.4 Synthesis procedure of SEGPHOS 71 2.6.5 Synthesis procedure of Ph-BPE 72 2.6.6 Synthesis procedure of TangPhos 73 2.6.7 Synthesis procedure of Binaphane 74 2.7 Concluding remarks 75 References 75 3 Design and Synthesis of Phosphite Ligands for Homogeneous Catalysis 81 Aitor Gual, Cyril Goddard, Verónica de la Fuente, and Sergio Castillón 3.1 Introduction 81 3.2 Synthesis of phosphites 82 3.2.1 Monophosphites 82 3.2.1.1 Symmetrically substituted monophosphites 82 3.2.1.2 Nonsymmetrically substituted monophosphites 83 3.2.1.3 Caged monophosphites 84 3.2.1.4 Monophosphites bearing dioxaphospho-cyclic units 84 3.2.2 Diphosphite ligands 94 3.2.2.1 Diphosphites not containing a dioxaphospho-cyclic unit 94 3.2.2.2 Diphosphites bearing dioxaphospho-cyclic units 95 3.2.3 Triphosphites 105 3.3 Highlights of catalytic applications of phosphite ligands 106 3.3.1 Hydrogenation reactions 106 3.3.2 Functionalization of alkenes: hydroformylation and hydrocyanation 108 3.3.2.1 Hydroformylation 108 3.3.2.2 Hydrocyanation 110 3.3.3 Addition of nucleophiles to carbonyl compounds and derivatives 110 3.3.3.1 1,2-addition 111 3.3.3.2 1,4-addition 111 3.3.4 Allylic substitution reactions 113 3.3.5 Miscellaneous reactions 117 3.4 General synthetic procedures 122 3.4.1 Symmetrically substituted phosphites 122 3.4.2 Nonsymmetrically substituted phosphites 123 3.4.3 Phosphites bearing dioxaphospho-cyclic units 123 References 124 4 Phosphoramidite Ligands 133 Laurent Lefort and Johannes G. de Vries 4.1 Introduction 133 4.1.1 History 134 4.2 Synthesis of phosphoramidites 134 4.3 Reactivity of the phosphoramidites 135 4.4 Types of phosphoramidite ligands 136 4.4.1 Acyclic monodentate phosphoramidites 136 4.4.2 Cyclic monodentate phosphoramidites based on diols 136 4.4.2.1 Synthesis of binaphthol- and biphenol-based phosphoramidites 137 4.4.2.2 Synthesis of TADDOL-based phosphoramidites 140 4.4.2.3 Synthesis of spiro-based phosphoramidites 141 4.4.2.4 Synthesis of 1,2-diol-based phosphoramidites 141 4.4.2.5 Phosphoramidites based on unusual diols 141 4.4.3 Cyclic phosphoramidites based on amino alcohols 142 4.4.4 Bis-phosphoramidites 143 4.4.4.1 Bis-phosphoramidites based on diamines 143 4.4.4.2 Bis-phosphoramidites based on diols 144 4.4.4.3 Other bidentate phosphoramidites 145 4.4.5 Mixed bidentate ligands 145 4.4.5.1 Phosphoramidite–phosphines 145 4.4.5.2 Phosphoramidite–phosphite 147 4.4.5.3 Phosphoramidite–amines 148 4.4.5.4 Other bidentate phosphoramidite ligands 149 4.4.6 Polydendate phosphoramidites 149 4.5 Conclusion 153 4.6 Synthetic procedures 153 References 153 5 Phosphinite and Phosphonite Ligands 159 T. V. (Babu) RajanBabu 5.1 Introduction 159 5.2 General methods for synthesis of complexes 160 5.3 Syntheses and applications of phosphinite ligands 162 5.3.1 Early studies 162 5.3.2 Phosphinite ligands from carbohydrates 163 5.3.2.1 Rh-catalyzed asymmetric hydrogenation of dehydroaminoacids 164 5.3.2.2 Ni(0)-catalyzed asymmetric hydrocyanation 166 5.3.2.3 Ni(0)- and Pd(0)-catalyzed allylic substitution by carbon nucleophiles 170 5.3.2.4 Rh(I)-catalyzed hydroformylation of vinylarenes 171 5.3.2.5 Ni(II)-catalyzed asymmetric hydrovinylation of alkenes 171 5.3.2.6 Ligands for homogeneous catalysis in water 172 5.3.3 Phosphinite ligands from other alcohols 172 5.3.4 Phosphine–phosphinite and amine–phosphinite ligands 173 5.3.5 Phosphinites from amines, amino alcohols, and amino acids 174 5.3.5.1 Aminophosphines 174 5.3.5.2 Aminophosphine–phosphinite (AMPP) ligands 176 5.3.6 Bisphosphinite ligands with other scaffoldings 179 5.3.7 1,1'-Diaryl-2,2'-phosphinites and dynamic conformational control in asymmetric catalysis 180 5.3.8 Monophosphinite ligands 182 5.3.9 Hybrid ligands containing phosphinites 182 5.3.9.1 Thioether–phosphinite ligands 182 5.3.9.2 Oxazoline–phosphinite and pyridine–phosphinite ligands 184 5.3.9.3 An alkene–phosphinite ligand 186 5.3.9.4 Chiral transition metal Lewis acids bearing electron-withdrawing phosphinites 187 5.4 Synthesis and applications of phosphonite ligands 188 5.4.1 Early studies 188 5.4.2 Phosphonites from TADDOL and related compounds 189 5.4.3 Phosphonites derived from 2,2'-hydroxybiaryls and related compounds 193 5.4.4 Phosphine–phosphonite ligands 196 5.4.5 Phosphonites with paracyclophane backbone 196 5.4.6 Phosphonites with a spirobisindane backbone 197 5.4.7 Miscellaneous phosphonite ligands 198 5.4.8 Development of phosphonite ligands for industrially relevant processes 199 5.4.8.1 Phosphonite ligands in hydroformylation 199 5.4.8.2 Phosphonite ligands in Ni(0)-catalyzed hydrocyanation 201 5.4.8.3 Oxazoline–phosphonite ligands and olefin dimerization 203 5.4.9 Use of the phosphonite functionality to synthesize other ligands 206 5.5 Experimental procedures for the syntheses of prototypical phosphinite and phosphonite ligands 208 5.5.1 Phosphinite ligands 208 5.5.1.1 Me 2 P(OMe) 208 5.5.1.2 Et 2 POEt and EtP(OEt) 2 209 5.5.1.3 Synthesis of methyl 3,4-bis- O -[bis(3,5-dimethylphenyl)phosphino]- 2,6-di- O -benzoyl- a - D -glucopyranoside (Ligand 8) 209 5.5.1.4 Preparation of phenyl 2,3-bis- O -[bis[3,5-bis(trifluoromethyl) phenyl]-phosphino)-4,6- O -benzylidene-glucopyranoside 211 5.5.1.5 Preparation of bis-(pentafluorophenyl)chlorophosphine 212 5.5.1.6 An alternate general procedure for phosphinite incorporation. [(2S,3R)-3-phenylthio-4-methylpent-2-oxy]diphenylphosphine 212 5.5.1.7 Metal-template synthesis of an amino1,2-diarylphosphinediarylphophinite complex 213 5 5.5.1.8 Procedure for the preparation of a bis-aminodiaryphosphine (R)-37 213 5.5.1.9 (-)-(S)-4- tert -butyl-2-{1-di(2'-methylphenyl)phosphinite- 1-methyl-ethyl}-4,5-dihydro-oxazole 214 5.5.1.10 (R)-7-(2-phenyl-6,7-dihydro-5H-[1]pyrindin)-di-(2'-methylphenyl)- phosphinite 215 5.5.2 Phosphonite ligands 217 5.5.2.1 (IR,7R)-9,9-dimethyl-2,2,4,6.6-penta(2-naphthyl)-3,5,8,l0-tetraoxa- 4-phosphabicyclo[5.3.0]-decane 217 5.5.2.2 (IR,7R)-9,9-dimethyl-2,2,4,6.6-penta(2-naphthyl)-3,5,8,l0-tetraoxa- 4-phosphabicyclo/5.3.0]-decane 218 5.5.2.3 Synthesis of (S)-2-[2-(diphenylphosphino)phenyl]-1,3,2-dinaphtho [d1,2,f1,2]dioxaphosphe-pine 219 5.5.2.4 4,5-Bis{di[(2-tert-butyl)phenyl]phosphonito}-9,9-dimethylxanthene 219 5.6 Acknowledgments 221 Abbreviations 221 References 222 6 Mixed Donor Ligands 233 René Tannert and Andreas Pfaltz 6.1 Introduction: general design principles 233 6.2 Synthesis of bidentate P,X-ligands 235 6.2.1 P,N-ligands 235 6.2.1.1 Oxazoline-based P,N-ligands 235 6.2.1.2 Imidazoline-based P,N-ligands 243 6.2.1.3 Oxazole-, thiazole-, and imidazole-based P,N-ligands 243 6.2.1.4 Pyridine-based P,N-ligands 245 6.2.1.5 Amine- and imine-based P,N-ligands 247 6.2.1.6 Other P,N-ligands 250 6.2.2 P,O-ligands 250 6.2.3 P,S-ligands 252 6.2.4 P,C-ligands 255 6.3 Conclusion 257 6.4 Experimental procedures 257 6.4.1 Synthesis of PHOX ligand 257 6.4.2 Synthesis of NeoPHOX ligand 259 References 260 7 Phospholes 267 Duncan Carmichael 7.1 Introduction 267 7.2 Creation of phospholes for use as ligands 269 7.2.1 Reactions of phosphorus dihalides with metallated dienes 269 7.2.2 Reactions of phosphorus dihalides with dienes 270 7.2.3 Michael addition of primary phosphines to dienes 271 7.3 Postsynthetic functionalisation 271 7.3.1 Functionalisation at phosphorus 271 7.3.2 Use of electrophiles 272 7.3.3 Use of nucleophiles and aromatics 272 7.3.4 Elaboration about the phosphole nucleus 272 7.4 Phosphole coordination chemistry 273 7.5 Phospholes in catalysis 276 7.6 Experimental procedures 279 References 280 8 Phosphinine Ligands 287 Christian Müller 8.1 Introduction 287 8.2 Ligand properties 288 8.2.1 Electronic properties 288 8.2.2 Structural characteristics and steric properties 289 8.2.3 Reactivity of phosphinines 290 8.3 Synthesis of Phosphinines 292 8.3.1 O + /P exchange reaction 292 8.3.2 Tin route 294 8.3.3 [4 + 2] cycloaddition reactions 294 8.3.4 Ring expansion methods 295 8.3.5 Metal-mediated functionalizations 296 8.4 Coordination chemistry 297 8.5 Reactivity of transition metal complexes 300 8.6 Application of phosphinines in homogeneous catalysis 300 8.7 Experimental procedure for the synthesis of selected phosphinines 303 References 305 9 Highly Strained Organophosphorus Compounds 309 J. Chris Slootweg 9.1 Introduction 309 9.2 Three-membered rings 310 9.3 Rearrangements 312 9.4 Homogeneous catalysis 313 9.5 Conclusions 314 9.6 Experimental procedures 315 9.6.1 Synthesis of BABAR-Phos 49a (R = i-Pr) 315 9.6.2 Synthesis of BABAR-Phos 49b (R = 3,5-(CF3)2C6H3) 316 References 317 10 Phosphaalkenes 321 Julien Dugal-Tessier, Eamonn D. Conrad, Gregory R. Dake, and Derek P. Gates 10.1 Introduction 321 10.1.1 Frontier molecular orbitals of phosphaalkenes 322 10.2 Synthesis of phosphaalkenes 324 10.2.1 Diphosphinidenecyclobutene (DPCB) synthesis (P,P chelates) 324 10.2.2 Bidentate-chelating P,P phosphaalkene ligands 325 10.2.3 Phosphaalkenes capable of P,N-chelation to metals 326 10.2.4 P,X achiral phosphaalkene ligands (X=P, O, S) 326 10.2.5 Synthesis of enantiomerically pure P,X ligands (X=P, N) 328 10.3 Catalysis with phosphaalkene ligands 329 10.3.1 Ethylene polymerization 329 10.3.2 Cross-coupling reactions 330 10.3.3 Hydro- and dehydrosilylation 332 10.3.4 Hydroamination and hydroamidation 333 10.3.5 Isomerization reactions 334 10.3.6 Allylic substitution 335 10.3.7 Asymmetric catalysis 336 10.4 Concluding remarks 337 10.5 Experimental procedures for representative ligands 338 10.5.1 Synthesis of DPCB 338 10.5.2 Synthesis of PhAk–Ox 338 10.6 Acknowledgments 339 References 339 11 Phosphaalkynes 343 Christopher A. Russell and Nell S. Townsend 11.1 Introduction 343 11.2 General experimental 344 11.3 Preparation of PC t Bu 344 11.3.1 Tris(trimethylsilyl)phosphine, P(SiMe 3 ) 3 345 11.3.2 tert -butylphosphaalkene, Me 3 SiP = C(OSiMe 3 ) t Bu (systematic name [2,2-dimethyl-1-(trimethylsiloxy)propylidene]–(trimethylsilyl) phosphine) 346 11.3.3 (2,2-dimethylpropylidyne)phosphine; t BuC=P 347 11.4 Adamanylphosphaalkyne, AdC=P 348 11.4.1 Adamant-1-yl(trimethylsiloxy)methylidene (trimethylsilyl) phosphane 348 11.4.2 (Adamant-1-ylmethylidyne)phosphane 348 11.5 Mesitylphosphaalkyne, MesC=P 349 11.5.1 Preparation of potassium bis(trimethylsilyl)phosphide {KP(SiMe 3 ) 2 } 349 11.5.2 Mesityl(trimethylsiloxy)methylene trimethylsilylphosphane 349 11.5.3 Mesitylphosphaalkyne 350 11.6 Phospholide anions 350 11.6.1 Preparation of Cp 2 Zr(PC t Bu) 2 351 11.6.2 Preparation of ClP(PC t Bu) 2 351 11.6.3 Preparation of the triphospholide anion and derivation to give the triphenylstannylphosphole 352 11.6.4 Preparation of Cl 3 P 3 (C t Bu) 2 352 11.6.5 Preparation of the triphospholide anion 352 11.7 1,3,5-Triphosphabenzene 352 11.7.1 Preparation of Cl 3 VN t Bu 353 11.7.2 Preparation of 1,3,5-triphospabenzene; P 3 (C t Bu) 3 353 References 353 12 P-chiral Ligands 355 Jérôme Bayardon and Sylvain Jugé 12.1 Introduction 355 12.2 Designing P-chiral ligands using alcohols as chiral auxiliaries 357 12.3 Designing P-chiral ligands using amino alcohols as chiral auxiliaries 363 12.3.1 Synthesis starting from tricoordinated 1,3,2-oxazaphospholidines 363 12.3.2 Synthesis starting from tetracoordinated 1,3,2-oxazaphospholidines 364 12.3.3 Synthesis starting from 1,3,2-oxazaphospholidine borane complexes 366 12.3.3.1 Interest of the borane–phosphorus complex chemistry 366 12.3.3.2 Ephedrine method 366 12.3.3.3 Methyl phosphinite boranes as P-chiral electrophilic building blocks 367 12.3.3.4 Chlorophosphine boranes as P-chiral electrophilic building blocks 368 12.3.3.5 Designing P-chiral aminophosphine phosphinites (AMPP*) 371 12.3.3.6 P-chiral o -hydroxyaryl phosphines 371 12.3.3.7 P-chiral secondary phosphine boranes 373 12.3.3.8 P-chiral 1,2-diphosphinobenzenes 373 12.3.3.9 Strategies for the enantiodivergent synthesis of P-chiral ligands 375 12.4 Designing of P-chiral ligands using amines as chiral auxiliaries 377 12.4.1 Sparteine as chiral auxiliary 377 12.4.2 a -Arylethylamines as chiral auxiliaries 381 12.5 Conclusion 381 12.6 Experimental procedures 383 References 385 13 Phosphatrioxa-Adamantane Ligands 391 Paul G. Pringle and Martin B. Smith 13.1 Introduction 391 13.2 Synthesis of phosphatrioxa-adamantanes 393 13.3 Catalysis supported by phosphatrioxa-adamantane ligands 395 13.3.1 Alkoxycarbonylation 395 13.3.2 Hydroformylation and hydrocyanation 397 13.3.3 Pd-catalysed coupling reactions 399 13.3.4 Asymmetric hydrogenation 400 13.4 Experimental procedures for phosphatrioxa-adamantanes ligands 401 13.4.1 Preparation of CgPH 401 13.4.2 Preparation of CgPH(BH 3 ) 402 13.4.3 Preparation of CgPBr 402 13.4.4 Preparation of CgPCH 2 CH 2 CH 2 PCg (L1) 402 13.4.5 Preparation of CgPPh (L7) 402 References 402 14 Calixarene-based Phosphorus Ligands 405 Angelica Marson, Piet W. N. M. van Leeuwen, and Paul C. J. Kamer 14.1 Introduction 405 14.2 Conformational properties 407 14.3 Calixarene-based phosphorus ligands 409 14.3.1 Phosphines and phosphinites 409 14.3.2 Phosphites and phosphonites 414 14.4 Applications in homogeneous catalysis 422 14.5 Experimental procedures 424 References 425 15 Supramolecular Bidentate Phosphorus Ligands 427 Jarl Ivar van der Vlugt and Joost N. H. Reek 15.1 Introduction: general design principles 427 15.2 Construction of bidentate phosphorus ligands via self-assembly 429 15.2.1 H bonding 429 15.2.2 Metal template assembly 440 15.2.3 Ion templation 445 15.3 Conclusions 446 15.4 Experimental procedures 447 15.4.1 General remarks 447 15.4.2 Synthesis of UREAPhos 447 15.4.3 Synthesis of METAMORPhos 448 15.4.4 Synthesis of supraphos 450 References 459 16 Solid-phase Synthesis of Ligands 463 Michiel C. Samuels, Bert H. G. Swennenhuis, and Paul C. J. Kamer 16.1 Introduction 463 16.2 Insoluble supports in ligand synthesis 466 16.3 Soluble polymeric supports 470 16.4 Supported ligands in catalysis 472 16.5 Solid-phase synthesis of nonsupported ligands 473 16.6 Conclusions and outlook 475 16.7 Experimental procedures 476 References 478 17 Biological Approaches 481 René den Heeten, Paul C. J. Kamer, and Wouter Laan 17.1 Introduction 481 17.2 Peptide-based phosphine ligands 481 17.2.1 Solid-phase synthesis using phosphine-containing amino acids 481 17.2.1.1 Synthesis of phosphine-containing amino acids 482 17.2.1.2 Synthesis and application of phosphine-containing peptides 484 17.2.2 Functionalisation of peptides with phosphines 485 17.2.2.1 Phosphinomethylation of amines 485 17.2.2.2 Phosphine modification of peptides via imine or amide formation 485 17.3 Oligonucleotide-based phosphine ligands 487 17.3.1 Covalent anchoring of phosphines to DNA 487 17.4 Phosphine-based artificial metalloenzymes 488 17.4.1 Supramolecular anchoring of phosphines to proteins 489 17.4.1.1 Avidin–biotin 489 17.4.1.2 Antibodies 490 17.4.2 Covalent anchoring of phosphines 491 17.5 Conclusions and outlook 492 17.6 Representative synthetic procedures 493 17.6.1 Artificial hydrogenases based on the biotin–streptavidin technology 493 17.6.2 Site-selective covalent modification of proteins with phosphines via hydrazone linkage 494 17.7 Acknowledgments 495 References 495 18 The Design of Ligand Systems for Immobilisation in Novel Reaction Media 497 Paul B. Webb and David J. Cole Hamilton 18.1 Introduction 497 18.2 Aqueous biphasic catalysis 499 18.3 Fluorous biphasic catalysis 503 18.4 Ionic liquids as reaction media 507 18.5 Supercritical fluids as solvents in single- and multiphasic reaction systems 512 18.5.1 Biphasic systems based on CO2 516 18.6 Experimental section 518 18.6.1 Trisodium salt of 3,3′,3″-phosphinetriylbenzenesulfonic acid (TPPTS) 518 18.6.2 2,7-bis(SO3Na)-Xantphos 519 18.6.3 Sulfonated BINAP 519 18.6.4 Synthesis of Tris(1H,1H,2H,2H-perfluorooctyl)phosphine 520 18.6.5 Synthesis of Tris (4-tridecafluorohexylphenyl)phosphine 520 18.6.6 (Meta-sulfonatophenyl)diphenylphosphine, sodium salt (monosulfonated triphenylphosphine, TPPMS) 522 18.6.7 1-Propyl-3-methylimidazolium diphenyl(3-sulfonatophenyl)-phosphine ([PrMIM][TPPMS]) 523 18.6.8 4,4′-Phosphorylated 2,2′-Bis(diphenylphosphanyl)-1,1′-binaphthyl 523 18.6.9 Synthesis of (R)-6,6′-bis(perfluorohexyl)-2,2′ bis (diphenylphosphino)-1,1′-binaphthyl ((R)-Rf-BINAP) 524 References 526 Index

Read more less

a huge range and FREE tracked UK delivery on ALL orders.

Read more less

Book SynopsisOver the last decade, the area of homogeneous catalysis with transition metal has grown in great scientific interest and technological promise, with research in this area earning three Nobel Prizes and filing thousands of patents relating to metallocene and non-metallocene single site catalysts, asymmetric catalysis, carbon-carbon bond forming metathesis and cross coupling reactions. This text explains these new developments in a unified, cogent, and comprehensible manner while also detailing earlier discoveries and the fundamentals of homogeneous catalysis. Serving as a self-study guide for students and all chemists seeking to gain entry into this field, it can also be used by experienced researchers from both academia and industry for referring to leading state of the art review articles and patents, and also as a quick self-study manual in an area that is outside their immediate expertise. The book features: Topics including renewable feed stocks (biofuel, glycerol), carTable of Contents1. Chemical Industry and Homogeneous Catalysis1.1 Feed Stocks, Fuels and Catalysts1.2 Crude Oil to Gasoline and Basic Building Blocks by Heterogeneous catalysts1.3 Basic Building Blocks to Downstream Products by Homogeneous Catalysis1.4 Comparison among Different Types of Catalysis1.5 Catalyst Recovery1.6 Environmental IssuesProblemsBibliography2. Basic Chemical Concepts2.1 Ligands2.2 Metals2.3 Important Reaction TypesProblemsBibliography3. Methods of Investigation3.1 Catalytic cycle and intermediates3.2 Spectroscopic Studies3.3 Kinetic Studies3.4 Model Compounds3.5 Computational Techniques (Theoretical Calculation)3.6 Asymmetric CatalysisProblemsBibliography4. Carbonylation and Related Reactions4.1 Introduction4.2 Carbonylation and Manufacture of Acetic Acid4.3 Carbonylation of Other Alcohols4.4 Carbonylation of Methyl Acetate4.5 Carbonylation of Alkynes4.6 Other carbonylation and hydrocarboxylation reactions4.7 C1-Chemistry4.8 Engineering AspectsProblemsBibliography5. Hydrogenation and Other Hydrogen Based Catalytic Reactions5.1 Hydrogenation5.2 Hydroformylation5.3 Other Hydroformylation reactions5.4 Asymmetric Hydroformylation5.5 Hydrosilylation5.6 Hydrocyanation5.7 HydroaminationProblemsBibliography6. Polymerization and Selective Oligomerization of Alkenes6.1 Introduction6.2 Early Catalysts for Polyethylene and Polypropylene6.3 Modern Ziegler-Natta Catalyst6.4 Mechanistic Studies6.5 Single Site Catalysts6.6 Ethylene Polymerization with Polar comonomers6.7 Polymers of Other Alkenes6.8 Oligomerization of Ethylene6.9 Engineering AspectsProblemsBibliography7. Selective C-C Bond Forming Reactions With Alkenes7.1 Introduction7.2 Di-, Tri-, Tetramerization and Codimerization reactions7.3 Metathesis Reactions7.4 Pd-Catalyzed Cross Coupling Reactions7.5 Metal catalyzed Cyclopropanation and CycloadditionProblemsBibliography8. Oxidation8.1 Introduction8.2 Wacker Oxidation8.3 Metal-Catalyzed Liquid-Phase Autoxidation8.4 Polymers from Autoxidation Products8.5 Selective Oxidations8.6 Engineering and Safety ConsiderationsProblemsBibliography

Read more less

Book SynopsisOpens the door to the sustainable production of pharmaceuticals and fine chemicals Driven by both public demand and government regulations, pharmaceutical and fine chemical manufacturers are increasingly seeking to replace stoichiometric reagents used in synthetic transformations with catalytic routes in order to develop greener, safer, and more cost-effective chemical processes. This book supports the discovery, development, and implementation of new catalytic methodologies on a process scale, opening the door to the sustainable production of pharmaceuticals and fine chemicals. Pairing contributions from leading academic and industrial researchers, Sustainable Catalysis focuses on key areas that are particularly important for the fine chemical and pharmaceutical industries, including chemo-, bio-, and organo-catalytic approaches to C?H, C?N, and C?C bond-forming reactions. Chapters include academic overviews of current innovations and industrial case stuTrade Review“In brief, I have read this book with pleasure and I recommend it to all chemists working or getting started in the field of catalysis.” (Angew. Chem. Int. Ed., 1 October 2014) Table of ContentsForeword vii Preface ix Contributors xi Abbreviations xiii 1 Catalytic Reduction of Amides Avoiding LiAlH4 or B2H6 1 Deborah L. Dodds and David J. Cole-Hamilton 2 Hydrogenation of Esters 37 Lionel A. Saudan 3 Synthesis of Chiral Amines Using Transaminases 63 Nicholas J. Turner and Matthew D. Truppo 4 Development of a Sitagliptin Transaminase 75 Jacob M. Janey 5 Direct Amide Formation Avoiding Poor Atom Economy Reagents 89 Benjamin M. Monks and Andrew Whiting 6 Industrial Applications of Boric Acid and Boronic Acid-Catalyzed Direct Amidation Reactions 111 Joanne E. Anderson, Jannine Cobb, Roman Davis, Peter J. Dunn, Russ N. Fitzgerald, and Alan J. Pettman 7 OH Activation for Nucleophilic Substitution 121 Jonathan M.J. Williams 8 Application of a Redox-Neutral Alcohol Amination in the Kilogram-Scale Synthesis of a GlyT1 Inhibitor 139 Martin A. Berliner 9 Olefin Metathesis: From Academic Concepts to Commercial Catalysts 163 Justyna Czaban, Christian Torborg, and Karol Grela 10 Challenge and Opportunity in Scaling-up Metathesis Reaction: Synthesis of Ciluprevir (BILN 2061) 215 Nathan Yee, Xudong Wei, and Chris Senanayake 11 C–H Activation of Heteroaromatics 233 Koji Hirano and Masahiro Miura 12 The Discovery of a New Pd/Cu Catalytic System for C–H Arylation and Its Applications in a Pharmaceutical Process 269 Jinkun Huang, Xiang Wang, and Johann Chan 13 Diarylprolinol Silyl Ethers: Development and Application as Organocatalysts 287 Hiroaki Gotoh and Yujiro Hayashi 14 Organocatalysis for Asymmetric Synthesis: From Lab to Factory 317 Feng Xu 15 Catalytic Variants of Phosphine Oxide-Mediated Organic Transformations 339 Stephen P. Marsden 16 Formation of C–C Bonds Via Catalytic Hydrogenation and Transfer Hydrogenation 363 Joseph Moran and Michael J. Krische Index 409

Read more less

Book SynopsisServing as a user''s manual for synthetic organic and catalytic chemists, this book guides chemists in the design and choice of ligands to catalyze organic reactions and apply the results for more efficient, green, and practical synthesis. Focuses on the role of ligands in metal complexes that catalyze green organic transformations: a hot topic in the area of organic synthesis and green chemistry Offers a comprehensive resource to help readers design and choose ligands and understand selectivity/reactivity characteristics Addresses a gap by taking novel ligand approaches and including up-to-date discussion on hydrogen transfers and reactions Presents important industrial perspective and provides rational explanations of ligand effects, impacts, and noveltyTable of ContentsPreface ix Abbreviation xi Part I N-Heterocyclic Carbene Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 1 1 Oxidation and Hydrogenation Reactions Catalyzed by Transition Metal Complexes Bearing N-Heterocyclic Carbene Ligands 3 1.1 Introduction, 3 1.2 Oxidation of Alcohols Based on Hydrogen Transfer, 3 1.3 Oxidation of Alcohols Based on Dehydrogenation, 10 1.4 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds, 12 1.5 Other Related Hydrogenative Reactions, 21 References, 25 2 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing N-Heterocyclic Carbene Ligands 27 2.1 Introduction, 27 2.2 Carbon–Carbon Bond Formation Based on Hydrogen Transfer, 27 2.3 Carbon–Nitrogen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 37 2.4 Carbon–Oxygen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 46 References, 52 Part ii η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 55 3 Oxidation and Hydrogenation Catalyzed by Transition Metal Complexes Bearing η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands 57 3.1 Introduction, 57 3.2 Oxidation of Alcohol Based on Hydrogen Transfer and Dehydrogenation, 59 3.3 Oxidation of Amine Based on Hydrogen Transfer, 68 3.4 Hydrogenation and Transfer Hydrogenation of Carbonyl Compounds, 71 3.5 Hydrogenation and Transfer Hydrogenation of Imines and Related Compounds, 79 References, 84 4 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands 87 4.1 Introduction, 87 4.2 Carbon–Nitrogen Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 88 4.3 Carbon–Oxygen Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 97 4.4 Carbon–Carbon Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 102 References, 105 Part iii Pincer Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 107 5 Dehydrogenation of Alkanes Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 109 5.1 Introduction, 109 5.2 Conversion of Alkanes into Alkenes Based on Hydrogen Transfer, 109 5.3 Dehydroaromatization of Alkanes Based on Hydrogen Transfer, 115 5.4 Alkane Metathesis by Tandem Alkane Dehydrogenation and Alkene Metathesis, 118 5.5 Conversion of Alkanes into Alkenes Based on Dehydrogenation, 121 References, 126 6 Oxidation and Hydrogenation Reactions Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 128 6.1 Introduction, 128 6.2 Oxidation of Alcohols Based on Hydrogen Transfer and Dehydrogenation, 128 6.3 Dehydrogenation of Amines, 137 6.4 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds, 141 References, 157 7 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 159 7.1 Introduction, 159 7.2 Carbon–Carbon Bond Formation Based on Hydrogen Transfer, 159 7.3 Carbon–Nitrogen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 161 7.4 Carbon–Oxygen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 173 References, 182 Part iv Bidentate and Miscellaneous Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 183 8 Oxidation and Dehydrogenation of Alcohols and Amines Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 185 8.1 Introduction, 185 8.2 Oxidation of Alcohols Based on Hydrogen Transfer with Oxidant, 185 8.3 Dehydrogenative Oxidation of Alcohols without Oxidant, 209 8.4 Oxidation of Amines Based on Hydrogen Transfer and Dehydrogenation, 220 References, 224 9 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 228 9.1 Introduction, 228 9.2 Hydrogenation and Transfer Hydrogenation of Carbonyl and Related Compounds, 229 9.3 Hydrogenation and Transfer Hydrogenation of Imines and Related Compounds, 263 References, 274 10 Bond-Forming Reactions Based on Hydrogen Transfer Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 278 10.1 Introduction, 278 10.2 Carbon–Carbon Bond-Forming Reactions Based on Hydrogen Transfer, 279 10.3 Carbon–Nitrogen Bond-Forming Reactions Based on Hydrogen Transfer, 296 10.4 Carbon–Oxygen Bond-Forming Reactions Based on Hydrogen Transfer, 321 References, 330 Index 335

Read more less

Book SynopsisFour decades of landmark discoveries in heterogeneous catalysis Presenting an historical record of four decades of landmark research, this book draws together an important collection of heterogeneous catalysis papers published by Professor Eli Ruckenstein and his colleagues. One of the most prolific leaders in the field of heterogeneous catalysis today, Dr. Ruckenstein has pioneered methods in catalysis, surface chemistry, and materials science that are now used to develop new chemicals, energy sources, and materials. Heterogeneous Catalysis offers new insights into the underlying mechanisms and chemistry of heterogeneous catalysis. Moreover, the book will help readers develop new applications for both basic research and industry. Coverage includes: Catalysts in various reactions including methane CO2 reforming, methane partial oxidation, and catalytic combustion Applications of materials such as zeolites, meTable of Contents1 Catalytic conversion of methane to synthesis gas by CO2 reforming 1 2 Catalytic conversion of methane to synthesis gas by partial oxidation 79 3 Catalytic combustion of clean as well as nitrogen bound fuels over transitional metal oxides 139 4 Zeolites and their applications as catalysts and/or catalyst supports 223 5 Synthesis of mesoporous V-Mg-O oxides and their applications as catalysts 365 6 Synthesis of polymer supported catalysts and polymer-coated silica supports and their applications in catalysis 404 7 Metal sintering during heating in various atmospheres 473 8 Heterogeneous catalysis – a theoretical approach 667

Read more less

Book SynopsisThis book is based on a graduate course and suitable as a primer for any newcomer to the field, this book is a detailed introduction to the experimental and computational methods that are used to study how solid surfaces act as catalysts.Table of ContentsPreface viii 1 Heterogeneous Catalysis and a Sustainable Future 1 2 The Potential Energy Diagram 6 2.1 Adsorption, 7 2.2 Surface Reactions, 11 2.3 Diffusion, 13 2.4 Adsorbate–Adsorbate Interactions, 15 2.5 Structure Dependence, 17 2.6 Quantum and Thermal Corrections to the Ground-State Potential Energy, 20 3 Surface Equilibria 26 3.1 Chemical Equilibria in Gases, Solids, and Solutions, 26 3.2 The Adsorption Entropy, 31 3.3 Adsorption Equilibria: Adsorption Isotherms, 34 3.4 Free Energy Diagrams for Surface Chemical Reactions, 40 Appendix 3.1 The Law of Mass Action and the Equilibrium Constant, 42 Appendix 3.2 Counting the Number of Adsorbate Configurations, 44 Appendix 3.3 Configurational Entropy of Adsorbates, 44 4 Rate Constants 47 4.1 The Timescale Problem in Simulating Rare Events, 48 4.2 Transition State Theory, 49 4.3 Recrossings and Variational Transition State Theory, 59 4.4 Harmonic Transition State Theory, 61 5 Kinetics 68 5.1 Microkinetic Modeling, 68 5.2 Microkinetics of Elementary Surface Processes, 69 5.3 The Microkinetics of Several Coupled Elementary Surface Processes, 74 5.4 Ammonia Synthesis, 79 6 Energy Trends in Catalysis 85 6.1 Energy Correlations for Physisorbed Systems, 85 6.2 Chemisorption Energy Scaling Relations, 87 6.3 Transition State Energy Scaling Relations in Heterogeneous Catalysis, 90 6.4 Universality of Transition State Scaling Relations, 93 7 Activity and Selectivity Maps 97 7.1 Dissociation Rate-Determined Model, 97 7.2 Variations in the Activity Maximum with Reaction Conditions, 101 7.3 Sabatier Analysis, 103 7.4 Examples of Activity Maps for Important Catalytic Reactions, 105 7.4.1 Ammonia Synthesis, 105 7.4.2 The Methanation Reaction, 107 7.5 Selectivity Maps, 112 8 The Electronic Factor in Heterogeneous Catalysis 114 8.1 The d-Band Model of Chemical Bonding at Transition Metal Surfaces, 114 8.2 Changing the d-Band Center: Ligand Effects, 125 8.3 Ensemble Effects in Adsorption, 130 8.4 Trends in Activation Energies, 131 8.5 Ligand Effects for Transition Metal Oxides, 134 9 Catalyst Structure: Nature of the Active Site 138 9.1 Structure of Real Catalysts, 138 9.2 Intrinsic Structure Dependence, 139 9.3 The Active Site in High Surface Area Catalysts, 143 9.4 Support and Structural Promoter Effects, 146 10 Poisoning and Promotion of Catalysts 150 11 Surface Electrocatalysis 155 11.1 The Electrified Solid–Electrolyte Interface, 156 11.2 Electron Transfer Processes at Surfaces, 158 11.3 The Hydrogen Electrode, 161 11.4 Adsorption Equilibria at the Electrified Surface–Electrolyte Interface, 161 11.5 Activation Energies in Surface Electron Transfer Reactions, 162 11.6 The Potential Dependence of the Rate, 164 11.7 The Overpotential in Electrocatalytic Processes, 167 11.8 Trends in Electrocatalytic Activity: The Limiting Potential Map, 169 12 Relation of Activity to Surface Electronic Structure 175 12.1 Electronic Structure of Solids, 175 12.2 The Band Structure of Solids, 179 12.3 The Newns–Anderson Model, 184 12.4 Bond-Energy Trends, 186 12.5 Binding Energies Using the Newns–Anderson Model, 193 Index 195

Read more less

Book SynopsisThe development of new asymmetric catalytic methods is of fundamental importance to industrial synthetic chemistry. The demand for optically pure synthetic intermediates and the drive to adopt greener methods of synthesis have stimulated a growing interest in biocatalysis as a selective and environmentally benign synthetic technique. Practical Biotransformations: A Beginner''s Guide provides an introduction to microbes and enzymes and demonstrates their practical applications in synthetic organic chemistry. Designed as a laboratory manual, this user-friendly guide discusses standard laboratory techniques, with appropriate advice on aspects of microbial practice and associated safety. Topics covered include: An introduction to equipment in a biotransformations laboratory An overview of biocatalyst sources Maintenance and growth of biocatalysts Example biotransformations using commerciaTrade Review?The book provides a good overview and appropriately conceived outline of this complex topic, enabling the interested reader to begin work with enzymes quickly and without unnecessary complications.? (Angewandte Chemie, October 2009) ?Gogan presents a beginner's guide to microbes and enzymes and how to use them for synthetic organic reactions in the laboratory.? ( Book News, September 2009) ?This book is easy to read and well organized and can be dipped in and out of, depending on your level of experience in different areas. ? Overall and excellent, interesting and user-friendly manual/textbook.? (Chemistry World, August 2009) Table of ContentsChapter 1: Biotransformations, Microbes and Enzymes. 1.1 Introduction. 1.2 Biotransformations. 1.3 Microorganisms. 1.4 Organism nomenclature. 1.5 Enzymes. 1.6 Types of Enzymatic reactions. 1.7 Enzymatic Cofactors. 1.8 Some Basic Characteristics of Enzyme Catalysis. 1.9 Types of Biocatalyst - Biotransformations by ‘whole cells’ or isolated enzymes. 1.10. Conclusion. Chapter 2: An overview of biocatalyst sources and web-based information. 2.1 Introduction. 2.2 Microbial culture collections. 2.3 Obtaining organisms from other research groups. 2.4 Selective Enrichments. 2.5 Metagenomics. 2.6 Enzyme Suppliers and Biocatalyst Development Companies. 2.7 Genome mining for biocatalysts. 2.8 Obtaining amino acid and gene sequence information on biocatalysts. 2.9 Obtaining DNA templates for cloning. 2.10 Custom Gene Synthesis. 2.11 Other interesting web resources for biocatalysis. 2.12 Conclusion. Chapter 3: Setting up a laboratory for biotransformations. 3.1 Introduction. 3.2 Microbiological Containment. 3.3 On containment issues and genetically-modified organisms. 3.4 Equipment for handling microorganisms. 3.5 Techniques and terms in microbiology - Sterility, Asepsis and Aseptic Technique. 3.6 Disposal of viable microbial waste and disinfection of reusable equipment. 3.7 Equipment for enzymology and molecular biology. 3.8 General reagents and chemicals in a Biotransformations Laboratory. 3.9 Conclusion. Chapter 4: A beginner’s guide to preparative whole-cell microbial biotransformations. 4.1 Introduction. 4.2 Storage, maintenance and growth of microorganisms. 4.3 General Microbiological Methods. 4.4 Examples of Whole-cell Biotransformations using Bacteria. 4.5 Biotransformation by filamentous fungi and yeasts. 4.6 Whole-cell Biotransformations by recombinant strains of E. coli. 4.7 Conclusion. Chapter 5: A beginner’s guide to biotransformations by commercially available isolated enzymes. 5.1 Introduction. 5.2 Lipases. 5.3 Hydrolytic Reactions using lipases. 5.4 Using lipases for acylation reactions. 5.5 Other hydrolases. 5.6 Commercially available Coenzyme-dependent Enzymes. 5.7 Carbon-carbon bond forming reactions. 5.8 Conclusion. Chapter 6: A beginner’s guide to the isolation and analysis and use of home-grown enzyme biocatalysts. 6.1 Introduction. 6.2 Cell growth and harvesting. 6.3 Cell disruption. 6.4 A typical procedure for making a cell extract from a recombinant strain of E. coli. 6.5 Purification of enzymes - a brief guide. 6.6 Techniques for Protein Purification. 6.7 Isolation of recombinant enzymes using histidine tags. 6.8 Estimation of protein concentration. 6.9 Concentrating protein samples by centrifugation. 6.10 Analysis of protein samples by sodium dodecylsulfate polyacrylamide gel electrophoresis (SDS-PAGE). 6.11 Examples of enzyme assays. 6.12 Using home-grown enzymes for biotransformations ? Some recent examples. 6.13 Conclusion. Chapter 7: An introduction to basic gene cloning for the production of designer biocatalysts. 7.1 Introduction. 7.2 Background to gene cloning. 7.3 Gene amplification by polymerase chain reaction (PCR). 7.4 DNA fragment analysis by agarose electrophoresis. 7.5 Gene cloning. 7.6 Analysis by DNA sequencing. 7.7 Troubleshooting the gene amplification and cloning process. 7.8 Ligation-Independent Cloning. 7.9 Gene Expression in E. coli. 7.10 Conclusion. Chapter 8: Engineering Enzymes. 8.1 Introduction. 8.2 Site-directed or targted mutagenesis as a tool for investigating enzyme mechanism or altering catalytic attributes. 8.3 A site-directed mutagenesis experiment. Considerations and practise. 8.4 Engineering using random mutagenesis. Directed Evolution of Enzymes. 8.5 Combining rational and random mutagenesis for biocatalyst improvement. 8.6 Exploiting catalytic promiscuity for creating new enzyme activities. 8.7 Designing enzymes in silico. 8.8 Conclusion. Appendices. 1. Structures of the proteinogenic amino acids. 2. Structures of bases found in nucleic acids. 3. The Genetic Code. 4. Recipes for Microbiological Growth Media. 5. Biological buffers. 6. Ammonium sulphate fractionation table. 7. Restriction enzymes and restriction sites.

Read more less

Book SynopsisThis book provides a comprehensive overview of the field of plasma catalysis, regarded as a promising alternative to thermal processes for energy and environmental applications. It bridges the gap between the plasma and catalysis research communities, covering both the fundamentals of plasma catalysis and its application in environmental and energy research. The first section of the book offers a broad introduction to plasma catalysis, covering plasma-catalyst systems, interactions, and modeling. The core of the book then focuses on different applications, describing a wide range of plasma-catalytic processes in catalyst synthesis, environmental clean-up, greenhouse gas conversion and synthesis of materials for energy applications. Chapters cover topics ranging from removal of NOx and VOCs to conversion of methane, carbon dioxide and the reforming of ethanol and methanol.Written by a group of world-leading researchers active in the field, the book forms a valuable resource for scientists, engineers and students with different research backgrounds including plasma physics, plasma chemistry, catalysis, energy, environmental engineering, electrical engineering and material engineering.Table of Contents

Read more less

Book SynopsisCo-edited by world-renowned scientists in the field of catalysis, this book contains the cutting-edge in situ and operando spectroscopy characterization techniques operating under reaction conditions to determine a materials’ bulk, surface, and solution complex and their applications in the field of catalysis with emphasis on solid catalysts in powder form since such catalyst are relevant for industrial applications. The handbook covers from widely-used to cutting-edge techniques. The handbook is written for a broad audience of students and professionals who want to pursue the full capabilities available by the current state-of-the-art in characterization to fully understand how their catalysts really operate and guide the rational design of advanced catalysts. Individuals involved in catalysis research will be interested in this handbook because it contains a catalogue of cutting-edge methods employed in characterization of catalysts. These techniques find wide use in applications such as petroleum refining, chemical manufacture, natural gas conversion, pollution control, transportation, power generation, pharmaceuticals and food processing. fdsfdsTable of ContentsVibrational Spectroscopy.- Electron and Photoelectron Spectroscopy.- Electron Microscopy.- Particle Scattering.- X-Ray Methods.- Magnetic Resonances.- Transient and Thermal Methods.- Soft Operando.

Read more less

Book SynopsisThis book provides an overview of plasticizers, from the latest global research developments to the laws and regulations applied to their use. In addition the book details the author's recently developed methodology for a catalytic hydrogenation of phthalate plasticizers. It presents insights into the development of the catalytic phthalate hydrogenation from the reaction mechanism and catalyst characterization to pilot tests and its industrialization. Given its scope, the book will appeal to a broad readership, particularly professionals at universities and scientific research institutes, as well as practitioners in industry.Table of ContentsIntroduction.- Plasticizer Laws and Evolution in Different Regions.- Current Status of Plasticizer Research.- Inventions and Patents in Different Regions.- Catalytic Ring Hydrogenation of Phthalate Plasticizers.- Pilot Demonstrations and Industrialization.

Read more less

Book SynopsisThis book introduces readers to the preparation of metal nanocrystals and its applications. In this book, an important point highlighted is how to design noble metal nanocrystals at the atomic scale for energy conversion and storage. It also focuses on the controllable synthesis of water splitting electrode materials including anodic oxygen evolution reaction (OER) and cathode hydrogen evolution reaction (HER) at the atomic level by defect engineering and synergistic effect. In addition, in-situ technologies and theoretical calculations are utilized to reveal the catalytic mechanisms of catalysts under realistic operating condition. The findings presented not only enrich research in the nano-field, but also support the promotion of national and international cooperation.Table of ContentsOverviews of noble metal nanocrystals.- Advanced synthesis methods of noble metal nanocrystals.- Characterization methods for noble metal nanocrystals.- Applications of noble metal nanocrystals.- Electrocatalytic water splitting technology.- Conclusions.

Read more less

Book SynopsisThis book describes the development of two kinds of continuous-flow transformation using heterogeneous catalysts, and explains how they can be applied in the multistep synthesis of active pharmaceutical ingredients. It demonstrates and proves that fine chemicals can be synthesized under continuous-flow conditions using heterogeneous catalysis alone. Importantly, the book also proposes a general concept and strategy for achieving multistep flow synthesis and developing heterogeneous catalysts, and shows that commercially available anion exchange resin can be used as a water-tolerant strong base catalyst for various types of continuous-flow aldol-type reaction. Reviewing the state of the art in heterogeneous catalysis in flow chemistry – a “hot topic” and rapidly developing area of organic synthesis – the book will provide readers with a deeper understanding of fine chemical flow synthesis and its future prospects. Table of Contents1. Introduction and Strategy.- 2. Synthesis of Nitro-containing Compounds through Multistep Continuous-flow with Heterogeneous Catalysts.- 3. Polysilane-Supported Pd Catalysts for Continuous-flow Hydrogenations.- 4. Anion Exchange Resins as Catalysts for Direct Aldol-type Reactions of Ketones, Esters and Nitriles under Continuous-flow.- 5. Multistep Continuous-flow Synthesis of APIs Based on Aldol-hydrogenation Strategy.- 6. Summary.- 7. Experimental Section.

Read more less

a huge range and FREE tracked UK delivery on ALL orders.

Read more less

a huge range and FREE tracked UK delivery on ALL orders.

Read more less

a huge range and FREE tracked UK delivery on ALL orders.

Read more less

a huge range and FREE tracked UK delivery on ALL orders.

Read more less

a huge range and FREE tracked UK delivery on ALL orders.

Read more less

Book SynopsisBringing together current advances and in-depth reviews of bio-based industrial products and agricultural biotechnology, Biocatalysis and Molecular Engineering examines the recent energy and food crises and points out the importance of using bio-based products from renewable resources and agricultural biotechnology.Table of ContentsPreface. Contributors. Section I. Improvement of Agronomic and Microbial Traits. 1.Insights into the Structure and Function of Acyl-CoA: Diacylglycerol Acyltransferase (Rodrigo M.P. Siloto, Qin Liu, Randall J. Weselake, Xiaohua He, and Thomas McKeon). 2. Improving Enzyme Character by Molecular Breeding: Preparation of Chimeric Genes (Kiyoshi Hayashi, Motomitsu Kitaoka, and Mamoru Nishimoto). 3. Production and Accumulation of Unusual Fatty Acids in Plant Tissues (D. Hildebrand, J.R, Thoguru, S. Rao, R Li, and T. Hatanaka). 4. Preparation of Oleaginous Yeast by Genetic Modification and Its Potential Applications (Yasushi Kamisaka). 5. Improving Value of Oil Palm Using Genetic Engineering (Ghulam Kadir Admad Parveez, Abrizah Othman, Umi Salamah Ramli, Ravigadevi Sambanthamurthi, Abdul Masani Mat Yunus, Ahmad Tarmizi Hashim, Ahmad Kushairi Din, and Mohd Basri Wahid). 6. Potential in Using Arabidopsis Acyl-Coenzyme-A-Binding Proteins in Engineering Stress-Tolerant Plants (Mee-Len Chye, Shi Xiao, Qin-Fang Chen, and Wei Gao). 7. Modification of Lipid Composition by Genetic Engineering in Oleaginous Marine Microorganism, Thraustochytrid (Tsunehiro Aki, Hiroaki Iwasaka, Hirofumi Adachi, Maya Nanko, Hiroko Kawasaki, Seiji Kawamoto, Toshihide Kakizono, and Kazuhisa Ono). 8. Integrated Approaches to Manage Tomato Yellow Leaf Curl Viruses (R. C, de la Peña, P. Kadirvel, S. Venkatesan, L. Kenyon, and J. Hughes). 9. Carbohydrate Acquisition During Legume Seed Development (Jocelyn A. Ozga, Dennis M. Reinecke, and Pankaj K. Bhowmik). 10. Biotechnology Enhancement of Phytosterol Biosynthesis in Seed Oils (Qilin Chen and Jitao Zou). Section II: Functional Foods and Biofuels. 11. Dietary Phosphatidylinositol in Metabolic Syndrome (Bungo Shirouchi, Koji Nagao, and Teruyoshi Yanagita). 12. Biotechnological Enrichment of Cereals with Polyunsaturated Fatty Acids (Milan Certik, Zuzana Adamechova, and Lucia Slavikova). 13. Lipophilic Ginsenoside Derivatives Production (Jiang-Ning Hu and Ki-Teak Lee). 14. Brown Seaweed Lipids as Possible Source for Nutraceuticals and Functonal Foods (M. Airanthi K. Widjaja-Adhi, Takayuki Tsukui, Masashi Hosokawa, and Kazuo Miysahita). 15. Processes for Production of Biodiesel Fuel (Yomi Watanabe and Yuji Shimada). 16. Noncatalytic Alcoholysis Process for Production of Biodiesel Fuel: Its Potential in Japan and Southeast Asia (Hiroshi Nabetani, Shoji Hagiwara, and Mitsutoshi Nakajima). 17. Use of Coniochaeta ligniaria to Detoxify Fermentation Inhibitors Present in Cellulosic Sugar Streams (Nancy N. Nichols, Bruce S. Dien, Maria J. López, and Joaquín Moreno). 18. Omics Applications to Biofuel Research (Tzi-Yuan Wang, Hsin-Liang Chen, Wen-Hsiung Li, Huang-Mo Sung, and Ming-Che Shih). Section III: Renewable Bioproducts. 19. Biotechnological Uses of Phospholipids (Jeong Jun Han, Jae Kwang Song, Joon Shick Rhee, and Suk Hoo Yoon). 20. Application of Partition Chromatographic Theory on the Routine Analysis of Lipid Molecular Species (Koretaro Takahashi and Tsugihiko Hirano). 21. Dehydrogenase-Catalyzed Synthesis of Chiral Intermediates for Drugs (Ramesh N. Patel). 22. Engineering of Bacterial Cycochrome P450 Monooxygenase as Biocatalysts for Chemical Synthesis and Environmental Bioremedication (Jun Ogawa, Quin-Shan Li, Sakayu Shimizu, Vlada Urlancher, and Rolf D. Schmid). 23. Glycosynthases from Inverting Hydrolases (Motomitsu Kitaoka). 24. Molecular Species of Diacylglycerols and Triacylglycerols Containing Dihydroxy Fatty Acids in Castor Oil (Jiann-Tsyh Lin). 25. Biocatalytic Production of Lactobionic Acid (Hirofumi Nakano, Takaaki Kiryu, Taro Kiso, and Hiromi Murakami). 26. Recent Advances in Aldolase-Catalyzed Synthesis of Unnatural Sugars and Iminocyclitols (Masakazu Sugiyama, Zhangyong Hong, William A. Greenberg, and Chi-Huey Wong). 27, Production of Value-Added Products by Lactic Acid Bacteria (Siqing Liu, Kenneth M. Bischoff, Yebo Li, Fengjie Cui, Hassan Azaizeh, and Ahmed Tafesh). 28. Enzymatic Synthesis of Glycosides Using Alpha-Amylase Family Enzymes (Kazuhisa Sugimoto, Takahisa Nishimura, Koji Nomura, Hiromi Nishiura, and Takashi Kuriki). 29. Biological Synthesis of Gold and Silver Nanoparticles Using Plant Leaf Extracts and Antimicrobial Application (Beom Soo Kim and Jae Yong Song). 30. Potential Approach of Microbial Conversion to Develop New Antifungal Products of Omega-3 Fatty Acids (Vivek K. Bajpai, Sun-Chul Kang, Hak-Ryul Kim, and Ching T. Hou). Index.

Read more less

Book SynopsisHomogeneous catalysis by soluble metal complexes has gained considerable attention due to its unique applications and features such as high activity and selectivity. Catalysis of this type has demonstrated impressive achievements in synthetic organic chemistry and commercial chemical technology. Homogeneous Catalysis with Metal Complexes: Kinetic Aspects and Mechanisms presents a comprehensive summary of the results obtained over the last sixty years in the field of the kinetics and mechanisms of organic and inorganic reactions catalyzed with metal complexes. Topics covered include: Specific features of catalytic reaction kinetics in the presence of various mono- and polynuclear metal complexes and nanoclusters Multi-route mechanisms and the methods of their identification, as well as approaches to the kinetics of polyfunctional catalytic systems Principles and features of the dynamic behavior of nonlinear kinetic models The potTable of ContentsNotations and Abbreviations xi Preface to English Edition xvii Preface xix Acknowledgments xxi About the Author xxiii Introduction 1 1 State-of-the-Art in the Theory of Kinetics of Complex Reactions 21 1.1 Main concepts of the Horiuti–Temkin theory of steady-state reactions 21 1.1.1 Reaction mechanism: Stoichiometry and routes 22 1.1.2 Kinetics: Reaction rates with respect to substances and over routes 32 1.1.3 Kinetic polynomial 42 1.1.4 Determining the number of independent parameters in a kinetic model. The problem of identifiability of parameters 44 1.2 Quasi-steady-state and quasi-equilibrium approximations in chemical kinetics 47 1.2.1 Theoretical criteria of quasi-steady-state intermediate concentrations and quasi-equilibrium steps 49 1.2.2 Experimental criteria of applicability of quasi-steady-state approximation in various systems 60 1.3 Methods of graph theory in chemical kinetics and in theory of complex reaction mechanisms 62 1.3.1 Linear mechanisms 62 1.3.2 Nonlinear mechanisms 71 1.3.3 Other fields of application of kinetic and bipartite graphs in chemical kinetics and in theory of complex reaction mechanisms 76 1.4 Elementary steps – Selection rules 79 1.4.1 Main postulates, laws, and principles 79 1.4.2 Energy selection rules for elementary steps 88 1.4.3 Quantum-chemical selection rules for elementary steps 92 1.4.4 Topological selection rules for elementary steps 108 References 113 2 Complexity Functions of Catalysts and Reactants in Reactions Involving Metal Complexes 121 2.1 Mononuclear metal complexes 122 2.1.1 Complexity functions: variants I and II 134 2.1.2 Complexity functions: variants III and IV 149 2.1.3 General problems and recommendations 165 2.2 Polynuclear complexes in homogeneous catalytic and noncatalytic reactions 167 2.2.1 Systems with formation of associates 168 2.2.2 Systems with mononuclear and polynuclear complexes of various types 182 2.3 Catalysis with polynuclear copper(I) halide complexes in superconcentrated solutions 193 2.3.1 Copper(I) chloride complexes in solution and in crystalline state 194 2.3.2 Kinetics of catalytic reactions of alkynes in concentrated NH4Cl–CuCl aqueous solutions at constant complexity functions FCu and FCl 203 2.3.3 Determination of compositions of catalytically active copper(I) complexes in various reactions 210 2.3.4 Studying π and σ complexes of copper(I) with alkynes in crystalline state and in solution 216 2.3.5 Mechanisms of acetylene dimerization and hydrocyanation reactions. Crystallochemical aspects 227 References 231 3 Multi-Route Mechanisms in Reactions Involving Metal Complexes 239 3.1 Factors accounting for the appearance and kinetic features of multi-route mechanisms 239 3.2 Analysis of multi-route reaction kinetics 246 3.3 Conjugation nodes and artificial multi-route character 271 3.4 Conjugate processes 304 3.4.1 Classical approach 305 3.4.2 Kinetic and thermodynamic conjugation in consecutive reactions 309 3.4.3 Conjugation in chain reactions 317 3.4.4 Conclusions 323 References 328 4 Polyfunctional Catalytic Systems 335 4.1 Oxidation reactions of organic and inorganic compounds 341 4.1.1 Oxidation of alkenes 341 4.1.2 Oxidation of 1,3-dienes 356 4.1.3 Oxidation of alkynes and arenes 366 4.1.4 Oxidation of inorganic compounds 369 4.2 Reactions of chlorination and oxidative chlorination of organic compounds 372 4.2.1 Oxidative chlorination of alkynes 372 4.2.2 Oxidative chlorination of 1,3-dienes 384 4.2.3 Polyfunctional catalytic systems in chlorination reactions 386 4.3 Oxidative carbonylation of organic compounds 389 4.3.1 Oxidative carbonylation of HY molecules (Y = OR, OPh, NR2, Ar, Alk) 390 4.3.2 Oxidative carbonylation of alkenes, dienes, and alkynes 400 4.4 Additive carbonylation of alkynes, alkenes, dienes, and alcohols 408 4.5 Substitution and addition reactions in alkyne chemistry 412 4.6 General problems in PFCS theory and practice 423 4.6.1 PFCSs and principles of their functioning 423 4.6.2 Kinetic and chemical functions of p-benzoquinone and other quinones in PFCSs 426 4.6.3 Variants of association of catalytic reactions and catalytic systems 436 References 442 5 Mechanisms of Formation of Catalytically Active Metal Complexes 453 5.1 Main stages of catalytic process 454 5.2 Chemical reactions involved in the formation of active centers 457 5.3 Mechanisms of active center formation in particular processes 468 5.3.1 Mechanisms of active metal complex formation in PdBr2 –LiBr–P(OPh)3–HBr–n-C4H9OH catalytic system for acrylate synthesis 468 5.3.2 Carbene metal complexes in metathesis of olefins and analogous processes 471 5.3.3 Mechanisms of 1-butene isomerization in Ni[P(OEt)3]4–H2SO4 –MeOH system 488 5.3.4 Features of the formation and decay of active centers in acrylic derivatives synthesis by the Reppe Method 490 5.3.5 Protecting active centers by catalytic process from destruction 492 5.3.6 Mechanism of active center formation in Pd(OAc)2 –PPh3 –p-benzoquinone–MeOH catalytic system for alkyne oxidative carbonylation at ≡C–H bond 494 5.3.7 Catalysis with small palladium(I) halide and carbonyl halide clusters 499 5.3.8 Mechanisms of formation of large cluster complexes and microheterogeneous nanoparticles 507 5.3.9 Synthesis and characterization of giant palladium clusters 512 5.3.10 Approaches to identification of the nature of catalytically active species in solutions of metal complexes 513 5.4 Examples of chain mechanisms and chain carriers of various natures 518 5.5 Classification of mechanisms of real catalytic processes 528 References 536 6 Nonlinear Effects (Critical Phenomena) in Reaction Dynamics in Homogeneous Catalysis with Metal Complexes 545 6.1 Historical notes 548 6.2 Physicochemical factors responsible for the critical phenomena in homogeneous reactions 551 6.2.1 Thermodynamic features of nonequilibrium processes near and far from equilibrium 552 6.2.2 Dynamic behavior of systems with linear mechanisms in open reactors with complete mixing 565 6.2.3 Nonlinearity of kinetic models 570 6.2.4 Main principles and methods of analysis of the dynamic behavior of nonlinear systems 573 6.3 Analysis of simple nonlinear kinetic models 582 6.4 Mechanisms of oscillatory catalytic reactions 630 6.4.1 Belousov–Zhabotinskii reaction (BZ reaction) 630 6.4.2 Liquid-phase oxidation of organic compounds by oxygen in Co(OAc)2–Br–CH3COOH system 640 6.4.3 Oxidative carbonylation of alkynes in solutions of palladium complexes 644 References 658 7 Rational Strategy for Designing Kinetic Models and Studying Complex Reaction Mechanisms 665 7.1 Stages in the development of chemical kinetics and methodological aspects of the strategy of studying complex reaction mechanisms 666 7.2 Alternative strategies for studying complex reaction mechanisms and designing kinetic models 669 7.2.1 Traditional strategy 669 7.2.2 Rational strategy 671 7.3 Hypothesis generation methods and examples 674 7.4 Hypothesis generation programs: Application examples and related problems 677 7.4.1 Combinatorics on kinetic graphs 677 7.4.2 ChemComb (Comb 1) program 686 7.4.3 MECHEM program 691 7.4.4 NetGen program 694 7.4.5 TAMREAC program 697 7.4.6 ChemNet program 697 7.4.7 Large reaction networks and problems in discrimination of hypotheses and construction of compact kinetic models 713 References 733 8 Effect of Medium on Reaction Rates in Homogeneous Catalysis with Metal Complexes 741 8.1 Effect of electrolytes on the activity coefficients of reaction medium components 743 8.2 Effect of electrolytes on the solubility of nonelectrolytes (gases and organic compounds) 748 8.3 Effect of electrolytes on the rates of elementary reactions between ions and uncharged substrates 752 8.4 Kinetics of catalytic reactions in concentrated aqueous electrolyte (HCl) solutions 754 8.5 Organic solvents in homogeneous catalysis with metal complexes 760 8.5.1 Main physical and chemical properties of solvents 760 8.5.2 Association of solvents and formation of molecular complexes 763 8.5.3 Metal complexes in organic and aqueous-organic solvents 765 8.5.4 Ion association, ion pairs, and specific salt effect in organic solvents 771 8.6 Strong protonic acids in organic solvents and kinetics of catalytic reactions with metal complexes in these media 775 8.6.1 Structure and properties of strong acid solutions in organic solvents 776 8.6.2 Kinetics of catalytic reactions in HCl–NMP, HCl–C2H5OH, and HCl–C2H5OH–CH3CN systems 783 8.7 Ionic liquids in catalytic chemistry 787 References 791 Conclusion 797 Subject Index 801 Index of Metals 803 Index of Reactions 805

Read more less

Book SynopsisPhotocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting. Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most important catalysts discovered today based on first and second row transition metals. A strong emphasis is placed on the description of their performance, as well as how they work from a mechanistic perspective. In addition, a theoretical description of some of the most relevant catalysts based on DFT are presented, as well as a description of related natural systems, such as the oxygen evoTable of ContentsList of Contributors xi Preface xv 1. Structural Studies of Oxomanganese Complexes for Water Oxidation Catalysis 1 Ivan Rivalta, Gary W. Brudvig, and Victor S. Batista 1.1 Introduction 1 1.2 Structural Studies of the OEC 2 1.3 The Dark-Stable State of the OEC 4 1.4 Biomimetic Oxomanganese Complexes 6 1.5 Base-Assisted O–O Bond Formation 7 1.6 Biomimetic Mn Catalysts for Artificial Photosynthesis 8 1.7 Conclusion 11 Acknowledgments 12 References 12 2. O–O Bond Formation by a Heme Protein: The Unexpected Efficiency of Chlorite Dismutase 15 Jennifer L. DuBois 2.1 Introduction 15 2.2 Origins of O2-Evolving Chlorite Dismutases (Clds) 15 2.3 Major Structural Features of the Proteins and their Active Sites 16 2.4 Efficiency, Specificity, and Stability 20 2.5 Mechanistic Insights from Surrogate Reactions with Peracids and Peroxide 22 2.6 Possible Mechanisms 23 2.7 Conclusion 25 Acknowledgements 25 References 25 3. Ru-Based Water Oxidation Catalysts 29 Laia Francàs, Roger Bofill, Jordi García-Antón, Lluis Escriche, Xavier Sala and Antoni Llobet 3.1 Introduction 29 3.2 Proton-Coupled Electron Transfer (PCET) and Water Oxidation Thermodynamics 31 3.3 O–O Bond Formation Mechanisms 33 3.4 Polynuclear Ru Water Oxidation Catalysts 34 3.5 Mononuclear Ru WOCs 40 3.6 Anchored Molecular Ru WOCs 42 3.7 Light-Induced Ru WOCs 43 3.8 Conclusion 45 Acknowledgments 46 References 46 4. Towards the Visible Light-Driven Water Splitting Device: Ruthenium Water Oxidation Catalysts with Carboxylate-Containing Ligands 51 Lele Duan, Lianpeng Tong, and Licheng Sun 4.1 Introduction 51 4.2 Binuclear Ru Complexes 52 4.3 Mononuclear Ru Complexes 54 4.3.1 Ru–O2N–N3 Analogs 55 4.3.2 Ru–O2N2–N2 Analogs 57 4.4 Homogeneous Light-Driven Water Oxidation 68 4.4.1 The Three-Component System 68 4.4.2 The Supramolecular Assembly Approach 69 4.5 Water Oxidation Device 72 4.5.1 Electrochemical Water Oxidation Anode 72 4.5.2 Photo-Anode for Water Oxidation 74 4.6 Conclusion 75 References 75 5. Water Oxidation by Ruthenium Catalysts with Non-Innocent Ligands 77 Tohru Wada, Koji Tanaka, James T. Muckerman, and Etsuko Fujita 5.1 Introduction 77 5.2 Water Oxidation Catalyzed by Dinuclear Ruthenium Complexes with NILs 81 5.3 Water Oxidation by Intramolecular O–O Coupling with [RuII2 (𝜇-Cl)(bpy)2(btpyan)]3+ 85 5.4 Mononuclear Ru–Aqua Complexes with a Dioxolene Ligand 91 5.4.1 Structural Characterization 91 5.4.2 Theoretical and Electrochemical Characterization 96 5.5 Mechanistic Investigation of Water Oxidation by Dinuclear Ru Complexes with NILs: Characterization of Key Intermediates 101 References 107 6. Recent Advances in the Field of Iridium-Catalyzed Molecular Water Oxidation 113 James A. Woods, Stefan Bernhard, and Martin Albrecht 6.1 Introduction 113 6.2 Bernhard 2008 [11] 114 6.3 Crabtree 2009 115 6.4 Crabtree 2010 116 6.5 Macchioni 2010 117 6.6 Albrecht/Bernhard 2010 117 6.7 Hetterscheid/Reek 2011 118 6.8 Crabtree 2011 119 6.9 Crabtree 2011 120 6.10 Lin 2011 120 6.11 Macchioni 2011 122 6.12 Grotjahn 2011 123 6.13 Fukuzumi 2011 123 6.14 Lin 2012 124 6.15 Crabtree 2012 125 6.16 Albrecht/Bernhard 2012 125 6.17 Crabtree 2012 126 6.18 Beller 2012 127 6.19 Lin 2012 128 6.20 Lloblet and Macchioni 2012 129 6.21 Analysis 130 References 131 7. Complexes of First Row d-Block Metals: Manganese 135 Philipp Kurz 7.1 Background 135 7.2 Oxidation States of Manganese in an Aqueous Environment 137 7.3 Dinuclear Manganese Complexes: Syntheses and Structures 138 7.4 Redox and Acid–Base Chemistry of Mn2-𝜇-WDL Systems 139 7.5 Mn2 Systems: Oxygen Evolution (but not Water Oxidation) Catalysis 142 7.6 Mn2 Complexes/the OEC/Ru2 Catalysts: A Comparison 144 7.7 Heterogeneous Water Oxidation Catalysis by Mn>2 Systems 146 7.8 Conclusion 148 Acknowledgements 148 References 149 8. Molecular Water Oxidation Catalysts from Iron 153 W. Chadwick Ellis, Neal D. McDaniel, and Stefan Bernhard 8.1 Introduction 153 8.2 Fe-Tetrasulfophthalocyanine 154 8.3 Fe-TAML 155 8.4 Fe-mcp 157 8.5 Fe2O3 as a Microheterogeneous Catalyst 158 8.6 Conclusion 160 References 161 9. Water Oxidation by Co-Based Oxides with Molecular Properties 163 Marcel Risch, Katharina Klingan, Ivelina Zaharieva, and Holger Dau 9.1 Introduction 163 9.2 CoCat Formation 164 9.3 Structure and Structure–Function Relations 166 9.4 Functional Characterization 173 9.5 Directly Light-Driven Water Oxidation 175 References 180 10. Developing Molecular Copper Complexes for Water Oxidation 187 Shoshanna M. Barnett, Christopher R. Waidmann, Margaret L. Scheuermann, Jared C. Nesvet, Karen Goldberg and James M. Mayer 10.1 Introduction 187 10.2 A Biomimetic Approach 188 10.2.1 Thermochemistry: Developing Oxidant/Base Combinations as PCET Reagents 189 10.2.2 Copper Complexes with Alkylamine Ligands 190 10.2.3 Copper Complexes with Anionic Ligands 195 10.2.4 Lessons Learned: Thermochemical Insights and Oxidant/Base Compatibility 198 10.3 An Aqueous System: Electrocatalysis with (bpy)Cu(II) Complexes 198 10.3.1 System Selection: bpy + Cu 199 10.3.2 Observing Electrocatalysis 199 10.3.3 Catalyst Turnover Number and Turnover Frequency 201 10.3.4 Catalyst Speciation: Monomer, Dimer, or Nanoparticles? 203 10.4 Conclusion 206 Acknowledgement 206 References 207 11. Polyoxometalate Water Oxidation Catalytic Systems 211 Jordan M. Sumliner, James W. Vickers, Hongjin Lv, Yurii V. Geletii, and Craig L. Hill 11.1 Introduction 211 11.2 Recent POM WOCs 214 11.3 Assessing POM WOC Reactivity 220 11.4 The Ru(bpy)3 2+ ∕S2O8 2-System 221 11.5 Ru(bpy) 3 3+ as an Oxidant for POM WOCs 222 11.6 Additional Aspects of WOC System Stability 224 11.7 Techniques for Assessing POM WOC Stability 224 11.8 Conclusion 227 Acknowledgments 228 References 228 12. Quantum Chemical Characterization of Water Oxidation Catalysts 233 Pere Miró, Mehmed Z. Ertem, Laura Gagliardi, and Christopher J. Cramer 12.1 Introduction 233 12.2 Computational Details 235 12.2.1 Density Functional Theory Calculations 235 12.2.2 Multiconfigurational Calculations 236 12.3 Methodology 237 12.3.1 Solvation and Standard Reduction Potentials 237 12.3.2 Multideterminantal State Energies 238 12.4 Water Oxidation Catalysts 238 12.4.1 Ruthenium-Based Catalysts 238 12.4.2 Cobalt-Based Catalysts 245 12.4.3 Iron-Based Catalysts 248 12.5 Conclusion 251 References 252 Index 257

Read more less

Book SynopsisThis book gradually brings the reader, through illustrations of the most crucial discoveries, into the modern world of chemical catalysis. Readers and experts will better understand the enormous influence that catalysis has given to the development of modern societies. Highlights the field''s onset up to its modern days, covering the life and achievements of luminaries of the catalytic era Appeals to general audience in interpretation and analysis, but preserves the precision and clarity of a scientific approach Fills the gap in publications that cover the history of specific catalytic processesTable of ContentsPreface ix 1 From the Onset to the First Large-Scale Industrial Processes 1 1.1 Origin of the Catalytic Era 1 1.2 Berzelius and the Affinity Theory of Catalysis 4 1.3 Discovery of the Occurrence of Catalytic Processes in Living Systems in the Nineteenth Century 6 1.4 Kinetic Interpretation of Catalytic Processes in Solutions: The Birth of Homogeneous Catalysis 8 1.5 Onset of Heterogeneous Catalysis 18 1.6 First Large-Scale Industrial Processes Based on Heterogeneous Catalysts 26 1.6.1 Sulfuric Acid Synthesis 26 1.6.2 Ammonia Problem 29 1.6.3 Ammonia Oxidation Process 32 1.6.4 Ammonia Synthesis 33 1.7 Fischer–Tropsch Catalytic Process 40 1.8 Methanol Synthesis 44 1.9 Acetylene Production and Utilization 46 1.10 Anthraquinone Process for Hydrogen Peroxide Production 47 References 49 2 Historical Development of Theories of Catalysis 59 2.1 Heterogeneous Catalysis 59 2.2 Chemical Kinetics and the Mechanisms of Catalysis 62 2.3 Electronic Theory of Catalysis: Active Sites 72 References 76 3 Catalytic Processes Associated with Hydrocarbons and the Petroleum Industry 83 3.1 Petroleum and Polymer Eras 83 3.2 Catalytic Cracking, Isomerization, and Alkylation of Petroleum Fractions 84 3.3 Reforming Catalysts 91 3.4 Hydrodesulfurization (HDS) Processes 93 3.5 Hydrocarbon Hydrogenation Reactions with Heterogeneous Catalysts 94 3.6 Olefin Polymerization: Ziegler–Natta, Metallocenes, and Phillips Catalysts 98 3.7 Selective Oxidation Reactions 109 3.7.1 Alkane Oxidation 109 3.7.2 Olefin Oxidation 110 3.7.3 Aromatic Compounds Oxidation 111 3.8 Ammoximation and Oxychlorination of Olefins 113 3.9 Ethylbenzene and Styrene Catalytic Synthesis 117 3.10 Heterogeneous Metathesis 118 3.11 Catalytic Synthesis of Carbon Nanotubes and Graphene from Hydrocarbon Feedstocks 119 References 121 4 Surface Science Methods in the Second Half of the Twentieth Century 131 4.1 Real Dispersed Catalysts versus Single Crystals: A Decreasing Gap 131 4.2 Physical Methods for the Study of Dispersed Systems and Real Catalysts 132 4.3 Surface Science of Single-Crystal Faces and of Well-defined Systems 139 References 147 5 Development of Homogeneous Catalysis and Organocatalysis 155 5.1 Introductory Remarks 155 5.2 Homogeneous Acid and Bases as Catalysts: G. Olah Contribution 156 5.3 Organometallic Catalysts 161 5.4 Asymmetric Epoxidation Catalysts 175 5.5 Olefin Oligomerization Catalysts 179 5.6 Organometallic Metathesis 180 5.7 Cross-Coupling Reactions 186 5.8 Pd(II)-Based Complexes and Oxidation of Methane to Methanol 190 5.9 Non-transition Metal Catalysis, Organocatalysis, and Organo-Organometallic Catalysis Combination 191 5.9.1 Metal-Free Hydrogen Activation and Hydrogenation 192 5.9.2 Amino Catalysis 193 5.10 Bio-inspired Homogeneous Catalysts 194 References 195 6 Material Science and Catalysis Design 205 6.1 Metallic Catalysts 205 6.2 Oxides and Mixed Oxides 208 6.2.1 SiO2 and SiO2-Based Catalysts and Processes 209 6.2.2 Al2O3 and Al2O3-Based Catalysts and Processes 211 6.2.3 SiO2–Al2O3− and SiO2–Al2O3-Based Catalysts and Processes 211 6.2.4 MgO− and MgO-Based Catalysts and Processes 212 6.2.5 ZrO2 and ZrO2-Based Catalysts and Processes 212 6.3 Design of Catalysts with Shape and Transition-State Selectivity 213 6.4 Zeolites and Zeolitic Materials: Historical Details 214 6.5 Zeolites and Zeolitic Materials Structure 218 6.6 Shape-Selective Reactions Catalyzed by Zeolites and Zeolitic Materials 221 6.6.1 Alkanes- and Alkene-Cracking and Isomerization 222 6.6.2 Aromatic Ring Positional Isomerizations 223 6.6.3 Synthesis of Ethyl Benzene, Cumene, and Alkylation of Aromatic Molecules 224 6.6.4 Friedel–Crafts Acylation of Aromatic Molecules 225 6.6.5 Toluene Alkylation with Methanol 225 6.6.6 Asaki Process for Cyclohexanol Synthesis 226 6.6.7 Methanol-to-Olefins (MTO) Process 226 6.6.8 Nitto Process 227 6.6.9 Butylamine Synthesis 227 6.6.10 Beckman Rearrangements on Silicalite Catalyst 227 6.6.11 Partial Oxidation Reactions Using Titanium Silicalite 227 6.6.12 Nylon-6 Synthesis: The Role of Zeolitic Catalysts 229 6.6.13 Pharmaceutical Product Synthesis 229 6.7 Organic–Inorganic Hybrid Zeolitic Materials and Inorganic Microporous Solids 230 6.7.1 Organic–Inorganic Hybrid Zeolitic Materials 230 6.7.2 ETS-10: A Microporous Material Containing Monodimensional TiO2 Chains 231 6.7.3 Hydrotalcites: Microporous Solids with Exchangeable Anions 232 6.8 Microporous Polymers and Metal–Organic Frameworks (MOFs) 232 6.8.1 Microporous Polymers 232 6.8.2 Metal–organic Frameworks 234 References 235 7 Photocatalysis 243 7.1 Photochemistry and Photocatalysis: Interwoven Branches of Science 243 7.2 Photochemistry Onset 245 7.3 Physical Methods in Photochemistry 249 7.4 Heterogeneous and Homogeneous Photocatalysis 251 7.5 Natural Photosynthesis as Model of Photocatalysis 253 7.6 Water Splitting, CO2 Reduction, and Pollutant Degradation: The Most Investigated Artificial Photocatalytic Processes 256 7.6.1 Water Splitting 257 7.6.2 CO2 Photoreduction 261 7.6.3 Photocatalysis in Environmental Protection 263 References 264 8 Enzymatic Catalysis 269 8.1 Early History of Enzymes 269 8.2 Proteins and Their Role in Enzymatic Catalysis 273 8.3 Enzymes/Coenzymes Structure and Catalytic Activity 284 8.4 Mechanism of Enzyme Catalysis 288 8.5 Biocatalysis 294 References 295 9 Miscellanea 299 9.1 Heterogeneous and Homogeneous Catalysis in Prebiotic Chemistry 299 9.2 Opportunities for Catalysis in the Twenty-First Century and the Green Chemistry 312 References 317 Index 321

Read more less