Mechanisms in homogeneous catalysis: a spectroscopic approach
Gespeichert in:
| Format: | Buch |
|---|---|
| Sprache: | English |
| Veröffentlicht: |
Weinheim
Wiley-VCH
2005
|
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis |
| Beschreibung: | XVI, 388 S. Ill., graph. Darst. |
| ISBN: | 3527310258 9783527310258 |
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CONTENTS 1 NMR SPECTROSCOPY AND HOMOGENEOUS CATALYSIS 1 ELOISA MARTINEZ
VIVIENTE, PAUL S. PREGOSIN, AND DANIELS SCHOTT 1.1 INTRODUCTION 1 1.2
REACTION MECHANISMS VIA REACTION MONITORING 3 1.2.1 DETECTING
INTERMEDIATES 3 1.2.2 REACTION KINETICS VIA NMR 9 1.3 STRUCTURAL TOOLS
14 1.3.1 CHEMICAL SHIFTS 14 1.3.2 COUPLING CONSTANTS 21 1.3.3 NOE
SPECTROSCOPY AND 3-D STRUCTURE 23 1.4 ISOTOPES IN CATALYSIS 27 1.4.1
KINETIC ISOTOPE EFFECT (KIE) 28 1.4.2 STRUCTURAL EFFECTS 29 1.4.3 AN
ACTIVE SITE COUNTING METHOD 31 1.5 DYNAMIC NMR SPECTROSCOPY 33 1.5.1
VARIABLE TEMPERATURE STUDIES 33 1.5.2 LINE SHAPE ANALYSIS 38 1.5.3
MAGNETIZATION TRANSFER 42 1.5.4 NOESY/EXSY/HIDDEN SIGNALS 43 1.6 SPECIAL
TOPICS 50 1.6.1 T X AND MOLECULAR H 2 COMPLEXES 50 1.6.2 PARAHYDROGEN
INDUCED POLARIZATION (PHIP) 5 1 1.6.2.1 HYDROGENATION MECHANISM STUDIES
52 1.6.2.2 PARAHYDROGEN AS A MAGNETIC PROBE 55 1.6.3 HIGH PRESSURE NMR
56 1.6.3.1 INTRODUCTION 56 1.6.3.2 APPLICATIONS 56 1.6.4 DIFFUSION AND
PULSED GRADIENT SPIN ECHO MEASUREMENTS 65 REFERENCES 71 2 HIGH PRESSURE
NMR CELLS 8? GABOR LAURENCZY AND LOTHAR HELM 2.1 INTRODUCTION 81
MECHANISMS IN HOMOGENEOUS CATALYSIS. A SPECTROSCOPIC APPROACH. EDITED BY
BRIAN HEATON COPYRIGHT 2005 WILEY-VCH VERLAG GMBH & CO. KGAA, WEINHEIM
ISBN 3-527-31025-8 X I CONTENTS 2.2 HIGH PRESSURE NMR OF LIQUIDS 83
2.2.1 HIGH PRESSURE, HIGH RESOLUTION PROBES 83 2.2.2 GLASS AND QUARTZ
CAPILLARIES 88 2.3 HIGH PRESSURE NMR OF SUPERCRITICAL FLUIDS 90 2.3.1
HIGH PRESSURE, HIGH TEMPERATURE NMR PROBES 90 2.3.2 TOROID PROBES FOR
HIGH PRESSURE NMR 93 2.4 HIGH PRESSURE NMR OF GASES DISSOLVED IN LIQUIDS
96 2.4.1 SAPPHIRE TUBES 96 2.4.2 HIGH PRESSURE PROBES FOR PRESSURIZED
GASES 200 2.5 CONCLUSIONS, PERSPECTIVES 102 ACKNOWLEDGMENTS 104
REFERENCES 105 3 THE USE OF HIGH PRESSURE INFRARED SPECTROSCOPY TO STUDY
CATALYTIC MECHANISMS 107 ANTHONY HAYNES 3.1 INTRODUCTION 107 3.2 CELL
DESIGN 108 3.2.1 TRANSMISSION CELLS 209 3.2.1.1 AMSTERDAM FLOW CELL 120
3.2.1.2 LOW-TEMPERATURE HP IR CELLS 222 3.2.1.3 HP IR CELLS FOR FLASH
PHOTOLYSIS 112 3.2.2 REFLECTANCE CELLS 224 3.3 MECHANISTIC STUDIES USING
HIGH PRESSURE IR SPECTROSCOPY 2 27 3.3.1 IN SITU STUDIES UNDER CATALYTIC
CONDITIONS 217 3.3.1.1 METHANOL CARBONYLATION 117 3.3.1.2
HYDROFORMYLATION 123 3.3.1.3 OTHER REACTIONS OF CARBON MONOXIDE 130
3.3.2 KINETIC AND MECHANISTIC STUDIES OF STOICHIOMETRIC REACTION STEPS
233 3.3.2.1 MIGRATORY CO INSERTION REACTIONS OF METAL ALKYLS 233 3.3.2.2
SUBSTITUTION AND EXCHANGE REACTIONS OF CO LIGANDS 138 3.3.2.3 EXCHANGE
BETWEEN RH-D AND H 2 140 3.3.2.4 HYDROGENOLYSIS OF M-C BONDS 140 3.3.2.5
MECHANISTIC STUDIES IN POLYMER MATRICES 242 3.3.2.6 NOBLE GAS AND H 2
COMPLEXES 142 3.3.2.7 ALKANE COMPLEXES AND C-H ACTIVATION REACTIONS 244
3.4 CONCLUSIONS 246 REFERENCES 247 4 PROCESSING SPECTROSCOPIC DATA 252
MARC GARLAND 4.1 INTRODUCTION 252 4.2 THE CATALYTIC SYSTEM 254 4.2.1
RECYCLE CSTR WITH ANALYTICS 254 4.2.2 PHYSICAL SYSTEM 156 CONTENTS XI
4.2.3 CHEMICAL DESCRIPTION 157 4.3 EXPERIMENTAL DESIGN 159 4.3.1
TRANSPORT TIME-SCALES 159 4.3.2 REACTION TIME-SCALES 160 4.3.2.1
SPECTROSCOPIC MEASUREMENTS 161 4.3.2.2 TIME-SCALES FOR SPECTROSCOPIC
MEASUREMENTS 162 4.3.3 THE MEANING OF "IN SITU" STUDIES 163 4.3.4 THE
PLANNING OF EXPERIMENTS 164 4.3.4.1 BATCH AND SEMI-BATCH 164 4.3.4.2
CHOICE OF SPECTROMETERS 164 4.3.4.3 GROUPS OF EXPERIMENTS 166 4.3.4.4
RANGE OF EXPERIMENTS 168 4.3.5 WELL-POSEDNESS AND ILL-POSEDNESS 168 4.4
DATA PRE-PROCESSING 169 4.4.1 DATA FILTERING AND OUTLIERS 269 4.4.2
SOLVENT AND REAGENT PURE COMPONENT SPECTRA 170 4.4.3 PRE-CONDITIONING
171 4.4.4 TRACK FINDING 173 4.4.5 CURVE FITTING 174 4.5 SPECTRAL
RECONSTRUCTION 276 4.5.1 HISTORICAL CONTEXT 176 4.5.2 ENTROPY
MINIMIZATION 176 4.5.2.1 ORGANOMETALLICS 177 4.5.2.2 CATALYSIS 179 4.5.3
BAND-TARGET ENTROPY MINIMIZATION 280 4.5.3.1 MULTIPLE-RUN,
PRECONDITIONED, MONOMETALLIC CATALYTIC DATA 282 4.5.3.2 MULTIPLE-RUN,
PRECONDITIONED, BIMETALLIC CATALYTIC DATA 282 4.5.3.3 SEMI-BATCH,
NON-PRECONDITIONED, MONOMETALLIC CATALYTIC DATA 184 4.5.3.4 SEMI-BATCH,
NON-PRECONDITIONED DATA: HRH(CO) 4 287 4.5.4 ADDITIONAL NOTES ON BTEM
287 4.6 CONCLUSIONS AND FUTURE DIRECTIONS 288 ACKNOWLEDGMENT 289
REFERENCES 2 90 5 CARBONYLATION OF METHANOL TO ACETIC ACID AND METHYL
ACETATE TO ACETIC ANHYDRIDE 195 GEORGE MORRIS 5.1 INTRODUCTION:
EVOLUTION OF CARBONYLATION PROCESSES 195 5.2 SOME IMPORTANT FEATURES OF
CARBONYLATION PROCESS CHEMISTRY 296 5.3 KEY STEPS IN THE MECHANISM OF
CARBONYLATION PROCESSES 299 5.4 INFORMATION FROM HP IR AND HP NMR FOR
CARBONYLATION REACTION STUDIES 202 5.4.1 STUDYING CARBONYLATION
MECHANISMS WITH IR AND HP IR 201 5.4.2 STUDYING CARBONYLATION MECHANISMS
WITH NMR AND HP NMR 204 XII CONTENTS 5.5 SPECTROSCOPIC STUDIES OF MODEL
REACTION STEPS OF THE RH CARBONYLATION CYCLE 205 5.5.1 MODEL STUDIES OF
OXIDATIVE ADDITION IN THE RH SYSTEM 206 5.5.2 MODEL STUDIES OF MIGRATORY
INSERTION IN THE RH SYSTEM 207 5.5.3 MODEL STUDIES OF REDUCTIVE
ELIMINATION IN THE RH SYSTEM 208 5.6 SPECTROSCOPIC STUDIES OF THE MODEL
REACTION STEPS OF THE IR CARBONYLATION CYCLE 209 5.6.1 MODEL STUDIES OF
OXIDATIVE ADDITION IN THE IR SYSTEM 209 5.6.2 MODEL STUDIES OF MIGRATORY
INSERTION IN THE IR SYSTEM 210 5.6.3 MODEL STUDIES OF REDUCTIVE
ELIMINATION IN THE IR SYSTEM 211 5.7 SPECTROSCOPIC STUDIES OF THE
ORGANIC CYCLES OF CARBONYLATION REACTIONS 212 5.7.1 NMR STUDIES OF AC 2
O AND ACL HYDROLYSIS 213 5.7.2 HP NMR STUDIES OF THE REACTION OF ACL
WITH MEOAC IN ANHYDROUS MEDIA 214 5.7.3 HP NMR STUDIES OF THE REACTION
OF HI WITH MEOAC IN AQUEOUS MEDIA 218 5.8 SPECTROSCOPIC STUDIES OF
WORKING CARBONYLATION REACTIONS 222 5.8.1 RH CATALYSED CARBONYLATION OF
MEOAC TO AC 2 O 223 5.8.2 RH CATALYSED CARBONYLATION OF MEOH TO ACOH 224
5.8.3 IR CATALYSED CARBONYLATION OF MEOH TO ACOH 226 5.9 CONCLUSIONS:
SPECTROSCOPY AND UNDERSTANDING CARBONYLATION MECHAN- ISMS 228
ACKNOWLEDGMENTS 228 REFERENCES 229 6 RHODIUM CATALYZED HYDROFORMYLATION
231 PAUL C. J. KAMER, JOOST N. H. REEK, AND PITT W. N. M. VAN LEEUWEN
6.1 INTRODUCTION 231 6.2 STUDY OF CATALYTIC RESTING STATES 233 6.3 IR
STUDIES ON LIGAND-FREE RHODIUM CARBONYL CATALYSTS 237 6.4 PHOSPHITE
LIGANDS 239 6.5 DIPHOSPHITE LIGANDS 244 6.6 DIMER FORMATION 250 6.7
STUDY OF BULKY PHOSPHORUS DIAMIDE LIGANDS 252 6.8 STUDY OF THE
ELEMENTARY STEPS OF THE CATALYTIC CYCLE 260 6.8.1 CO-DISSOCIATION 260
6.8.2 EXCHANGE BETWEEN RHD AND H 2 262 6.8.3 HYDRIDE MIGRATION 265 6.9
CONCLUSIONS 267 REFERENCES 267 7 ALKENE/CO COPOLYMERISATION 271 CLAUDIO
BIANCHINI AND ANDREA MELI 7.1 INTRODUCTION 271 CONTENTS XLIL 7.2
CATALYTIC CYCLES OF ALKENE/CO COPOLYMERISATION 274 7.2.1 MECHANISM OF
ETHENE/CO COPOLYMERISATION 274 7.2.1.1 METHANOL AND OTHER PROTIC
SOLVENTS 274 7.2.1.2 APROTIC SOLVENTS 276 7.2.1.3 FORMATION OF ACTIVE PD
SITES AND INITIATION OF ETHENE/CO COPOLYMERI- SATION 277 7.2.1 A CHAIN
PROPAGATION OF ETHENE/CO COPOLYMERISATION 279 7.2.1.5 IN SITU HIGH
PRESSURE NMR STUDIES OF ETHENE/CO COPOLYMERISATION IN PROTIC SOLVENTS
280 7.2.1.6 IN SITU HIGH PRESSURE NMR STUDIES OF CO/ETHENE
COPOLYMERISATION IN APROTIC SOLVENTS 282 7.2.1.7 IN SITU HIGH PRESSURE
IR STUDIES OF ETHENE/CO COPOLYMERISATION 284 7.2.1.8 MODEL SYNTHETIC
STUDIES OF ETHENE/CO COPOLYMERISATION 286 7.2.1.9 KINETIC AND
THERMODYNAMIC STUDIES OF ETHENE/CO COPOLYMERISATION IN APROTIC SOLVENTS
288 7.2.1.10 CHAIN TRANSFER IN ETHENE/CO COPOLYMERISATION 292 7.2.2
MECHANISM OF STYRENE/CO COPOLYMERISATION 297 7.2.3 MECHANISM OF
PROPENE/CO COPOLYMERISATION 301 7.2.4 MECHANISM OF CYCLIC ALKENES/CO
COPOLYMERISATION 302 7.2.5 MECHANISM OF POLAR ALKENES/CO
COPOLYMERISATION 304 7.2.6 CATALYST DEACTIVATION PATHS 305 REFERENCES
306 8 THE USE OF SPECTROSCOPY IN METALLOCENE-BASED POLYMERISATION
CATALYSIS 311 MANFRED BOCHMANN 8.1 INTRODUCTION 311 8.2 IDENTIFICATION
OF THE CATALYTICALLY ACTIVE SPECIES: THE CHEMISTRY OF GROUP 4 METAL
METHYL SPECIES 313 8.3 ACTIVATION OF ALTERNATIVE GROUP 4 CATALYST
PRECURSORS WITH B(C 6 F 5 ) 3 319 8.4 OLEFIN COORDINATION TO D METAL
CENTERS 323 8.5 ION PAIR DYNAMICS IN METALLOCENE CATALYSTS 328 8.6
MONOMER COORDINATION 333 8.7 POLYMERISATION KINETICS 335 8.8
SPECTROSCOPIC STUDIES ON COMPLEX SYSTEMS 339 8.9 SPECTROSCOPY OF
POLY(1-ALKENES): POLYPROPYLENE 344 8.10 CONCLUSION 352 REFERENCES 353 9
HYDROGENATIORT 359 RALF GIERNOTH 9.1 INTRODUCTION 359 9.2 THE DIHYDROGEN
MOLECULE 360 9.3 RHODIUM-CATALYZED HOMOGENEOUS HYDROGENATION, THE BASICS
360 9.3.1 THE ACHIRAL CASE 360 9.3.2 THE CHIRAL CASE 361 XIV CONTENTS
9.3.2.1 CATALYSTS 361 9.3.2.2 HYDRIDE ROUTE VERSUS UNSATURATE ROUTE 362
9.4 SPECTROSCOPIC METHODS 363 9.4.1 "STANDARD" NMR SPECTROSCOPY 363
9.4.2 PHIP-NMR-SPECTROSCOPY 365 9.4.2.1 ORTHO- AND PARAHYDROGEN 365
9.4.2.2 PARAHYDROGEN INDUCED POLARIZATION AND IN SITU SPECTROSCOPY 366
9.4.2.3 ALTADENA AND PASADENA 367 9.4.2.4 APPLICATIONS OF THE PHIP
METHOD 370 9.5 STUDYING THE CATALYTIC MECHANISM OF ENANTIOSELECTIVE
HYDROGENATION WITH NMR SPECTROSCOPIC METHODS 371 9.5.1 EARLY NMR
EXPERIMENTS: WILKINSON'S CATALYST REVISITED 371 9.5.2 THE MECHANISTIC
MODEL FOR THE CHIRAL CASE 371 9.5.3 DETECTION OF INTERMEDIATES WITH
STANDARD NMR SPECTROSCOPY 373 9.5.4 THE "BREAKTHROUGH": CHARACTERIZATION
OF THE KEY INTERMEDIATES WITH PHIP NMR SPECTROSCOPY 374 9.6 CONCLUSION
AND OUTLOOK 377 REFERENCES 377 INDEX 379 |
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| indexdate | 2025-02-10T13:13:44Z |
| institution | BVB |
| isbn | 3527310258 9783527310258 |
| language | English |
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| spelling | Mechanisms in homogeneous catalysis a spectroscopic approach ed. by Brian Heaton Weinheim Wiley-VCH 2005 XVI, 388 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier Catalysis Reaktionsmechanismus (DE-588)4177123-0 gnd rswk-swf Homogene Katalyse (DE-588)4160579-2 gnd rswk-swf Spektroskopie (DE-588)4056138-0 gnd rswk-swf (DE-588)4143413-4 Aufsatzsammlung gnd-content Homogene Katalyse (DE-588)4160579-2 s Reaktionsmechanismus (DE-588)4177123-0 s Spektroskopie (DE-588)4056138-0 s DE-604 Heaton, Brian Sonstige oth SWB Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=013104078&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Mechanisms in homogeneous catalysis a spectroscopic approach Catalysis Reaktionsmechanismus (DE-588)4177123-0 gnd Homogene Katalyse (DE-588)4160579-2 gnd Spektroskopie (DE-588)4056138-0 gnd |
| subject_GND | (DE-588)4177123-0 (DE-588)4160579-2 (DE-588)4056138-0 (DE-588)4143413-4 |
| title | Mechanisms in homogeneous catalysis a spectroscopic approach |
| title_auth | Mechanisms in homogeneous catalysis a spectroscopic approach |
| title_exact_search | Mechanisms in homogeneous catalysis a spectroscopic approach |
| title_full | Mechanisms in homogeneous catalysis a spectroscopic approach ed. by Brian Heaton |
| title_fullStr | Mechanisms in homogeneous catalysis a spectroscopic approach ed. by Brian Heaton |
| title_full_unstemmed | Mechanisms in homogeneous catalysis a spectroscopic approach ed. by Brian Heaton |
| title_short | Mechanisms in homogeneous catalysis |
| title_sort | mechanisms in homogeneous catalysis a spectroscopic approach |
| title_sub | a spectroscopic approach |
| topic | Catalysis Reaktionsmechanismus (DE-588)4177123-0 gnd Homogene Katalyse (DE-588)4160579-2 gnd Spektroskopie (DE-588)4056138-0 gnd |
| topic_facet | Catalysis Reaktionsmechanismus Homogene Katalyse Spektroskopie Aufsatzsammlung |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=013104078&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT heatonbrian mechanismsinhomogeneouscatalysisaspectroscopicapproach |