Aqueous organometallic catalysis (2001)

AQUEOUS ORGANOMETALLIC CATALYSIS by FERENC JOÓ Institute of Physical Chemistry, University of Debrecen and Research Group of Homogeneous Catalysis, Hungarian Academy of Sciences, Debrecen, Hungary KLUWER ACADEMIC PUBLISHERS NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW eBook ISBN: Print ISBN: 0-306-47510-3 1-4020-0195-9 ©2002 Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow Print ©2001 Kluwer Academic Publishers Dordrecht All rights reserved No part of this eBook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: and Kluwer's eBookstore at: http://kluweronline.com http://ebooks.kluweronline.com Preface Aqueous organometallic catalysis is a rapidly developing field and there are several reasons for the widespread interest Perhaps the most important is the possibility of using liquid-liquid two-phase systems for running catalytic reactions Often termed liquid biphasic catalysis, these two-phase procedures allow recycling of the catalyst dissolved exclusively in one of the phases – of course, this book focuses on the aqueous phase It is this catalyst recycling, together with the much simplified technology, where the interest of the chemical industry lies Small scale laboratory procedures may also benefit from using organometallic catalysts in aqueous solutions due to the easier, cleaner isolation of the desired products of biphasic reactions In addition, growing environmental concern forces industry and research laboratories to use less and less environmentally hazardous chemicals, and water –as opposed to most organics– is certainly an environmentally benign (green) solvent A somewhat less obvious and less exploited possibility is in that several catalytic reactions which take place in homogeneous aqueous solutions or in biphasic systems simply not happen in dry organic solvents This book is devoted to a systematic description of the basic phenomena, principles and practice of aqueous organometallic catalysis in a relatively concise and organised way Organisation of the material is not an easy task, since fundamental chemical questions, such as reactivity and selectivity of a catalyst in a given reaction should be treated together with the various synthetic applications and industrial or engineering aspects Only those systems are described where the catalyst itself is a genuine organometallic compound or where such intermediates are formed along the reaction pathway Accordingly, those organic syntheses in aqueous solutions where ix Preface x an organometallic compound acts as a stoichiometric reagent are largely omitted The field of liquid multiphase catalysis expands readily, nevertheless other multiphase techniques are just scarcely mentioned Among them phase transfer assisted organometallic catalysis is a special approach because there are many cases when the catalyst resides and acts in the aqueous phase or at the aqueous/organic interface Reactions, where the organometallic catalysis takes place entirely in the organic phase, and phase transfer catalysis is used merely to supply reagents from the aqueous phase are not discussed Numerous reviews, special journal editions and books have been already devoted to the topic of aqueous organometallic catalysis especially in the last 5-8 years All these publications, however, comprise of detailed reviews or accounts on particular topics written by leading specialists While this is certainly beneficial for those who themselves work in the same direction, non-specialists, students or those who are just to enter this field of research may be better served by a monograph of the style and size of the Catalysis by Metal Complexes series In 1994, in Volume 15 of this series, a chapter was published on aqueous organometallic hydrogenations – with the aim of giving a complete description of what had been done before in that respect After only seven years such an aim of all-inclusivity is irrealistic, and this had to bring with itself a selection of the literature used Writing of this book took much more time than originally expected I owe a lot of thanks to D J Larner, E M C Lutanie and J W Wijnen, Publishing Editors at Kluwer Academic Publishers who helped this long process by their advice and patience Thanks are due to the American Chemical Society, the Royal Society, Elsevier Science B V and WileyVCH Verlag GmbH for permissions to use previously published material All my family, colleagues and students had to survive the consequences of my preoccupation with this task – many thanks for their understanding I am particularly indebted to Gábor Papp for preparing the artwork Finally, and with utmost appreciation I thank the support and encouragement provided by my wife Dr Ágnes Kathó Without her understanding at home, and her invaluable help in literature search, proofreading and in discussions of the various versions of the manuscript this book could have never been completed Debrecen, September 2001 Ferenc Joó Table of Contents Preface ix Introduction 1.1 A personal look at the history of aqueous organometallic catalysis 1.2 General characteristics of aqueous organometallic catalysis References Ligands used for aqueous organometallic catalysis 2.1 Tertiary phosphine ligands with sulfonate or alkylene sulfate substituents 2.1.1 Direct sulfonation 2.1.2 Nucleophilic phosphinations, Grignard-reactions and catalytic cross-coupling for preparation of sulfonated phosphines 2.1.3 Addition reactions 2.2 Tertiary phosphine ligands with nitrogen-containing substituents 2.3 Phosphine ligands with carboxyl substituents 2.4 Hydroxyl-substituted water-soluble tertiary phosphines 2.5 Macroligands in aqueous organometallic catalysis 2.6 Bis[2-(diphenylphosphino)ethyl]amine - a versatile starting material for chelating bisphosphines 2.7 Tertiary phosphines with phosphonate and phosphonium substituents 2.8 Water-soluble ligands for aqueous organometallic catalysis latest developments 2.9 Solubilities of tertiary phosphines and their complexes in water References 11 Hydrogenation 3.1 Hydrogenation of olefins 3.1.1 Catalysts with simple ions as ligands 3.1.1.1 Ruthenium salts as hydrogenation catalysts v 12 13 16 20 21 24 25 27 32 32 32 39 40 47 49 49 49 vi 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.1.1.2 Hydridopentacyanocobaltate(III) 3.1.2 Water-soluble hydrogenation catalysts other than simple complex ions 3.1.2.1 Catalysts containing phosphine ligands 3.1.2.2 Hydrogenation of olefins with miscellaneous water-soluble catalysts without phosphine ligands 3.1.2.3 Mechanistic features of hydrogenation of olefins in aqueous systems 3.1.2.4 Water-soluble hydrogenation catalysts with macromolecular ligands 3.1.3 Enantioselective hydrogenations of prochiral olefins 3.1.4 Effect of amphiphiles on the enantioselective hydrogenation of prochiral olefins in water Hydrogenation of arenes and heteroarenes in aqueous systems Hydrogenation of aldehydes and ketones Hydrogenation of miscellaneous organic substrates 3.4.1 Hydrogenation of nitro compounds and imines Transfer hydrogenation and hydrogenolysis Hydrogenation of carbon dioxide in aqueous solution Hydrogenations of biological interest 3.7.1 Hydrogenation of biological membranes 3.7.2 Regeneration of dihydronicotinamide cofactors The water gas shift reaction and hydrogenations with mixtures 3.8.1 The water gas shift reaction 3.8.2 Hydrogenations with References 50 51 51 58 58 66 67 75 80 87 98 98 102 113 122 122 127 131 131 135 138 Hydroformylation 149 149 Introduction 4.1 4.2 Rhodium-catalyzed biphasic hydroformylation of olefins The Ruhrchemie-Rhône Poulenc process for manufacturing 152 butyraldehyde 4.3 Aqueous/organic biphasic hydroformylation butenes and other 156 alkenes 4.4 Basic research in aqueous organometallic hydroformylation; 157 ligands and catalysts 161 4.5 Mechanistic considerations 161 4.5.1 Effects of water vii 4.5.2 Effects of pH Asymmetric hydroformylation in aqueous media Surfactants in aqueous hydroformylation Water soluble polymeric ligands in aqueous hydroformylation 4.9 Aqueous extractions for efficient catalyst recovery 4.10 Synthetic applications 4.11 Miscellaneous aspects of aqueous-organic biphasic hydroformylation 4.11.1 Interphase engineering using “promoter ligands” 4.11.2 Gas-liquid-liquid reaction engineering References 4.6 4.7 4.8 164 166 167 172 176 179 184 184 185 185 Carbonylation 5.1 Introduction 5.2 Carbonylation of organic halides 5.3 Carbonylation of methane, alkenes and alkynes 5.4 Carbonylation of alcohols References 191 191 192 197 202 205 Carbon-carbon bond formation 6.1 Heck reactions in water 6.2 Suzuki couplings in aqueous media 6.3 Sonogashira couplings in aqueous media 6.4 Allylic alkylations in aqueous media 6.5 Catalytic removal of allylic protecting groups 6.6 Stille couplings in aqueous media 6.7 Other catalytic C-C bond formations 6.7.1 Miscellaneous reactions 6.7.2 Nucleophilic additions to 1,3-dienes; the synthesis of geranylacetone References 209 210 214 218 221 225 227 230 230 Dimerization, oligomerization and polymerization of alkenes and alkynes 7.1 Dimerization and polymerization of ethylene 7.2 Telomerization of dienes 7.3 Ring-opening metathesis polymerizations in aqueous media 7.4 Alkyne reactions 7.5 Alternating copolymerization of alkenes and carbon monoxide References 233 234 237 237 239 243 247 250 253 viii Catalytic oxidations in aqueous media - recent developments 8.1 Wacker-type oxidations 8.2 Oxidations with and References 257 257 260 262 Miscellaneous catalytic reactions in aqueous media 9.1 Aqueous organometallic catalysis under traditional conditions 9.2 Emerging techniques References 265 10 Host-guest chemistry in aqueous organometallic catalysis 10.1 Cyclodextrins and the formation of inclusion compounds 10.2 Application of cyclodextrins and other host molecules in aqueous organometallic catalysis References 279 Index Key to the abbreviations 291 301 265 274 275 279 281 289 Chapter Introduction 1.1 A personal look at the history of aqueous organometallic catalysis “Organometallic chemistry deals with moisture sensitive compounds therefore all manipulations should be carried out under strictly anhydrous conditions” – this was the rule of thumb ever since the preparation of the first organometallic compounds Not as if there were no isolated examples of water-stable organometallics from the very beginning, in fact Zeise`s salt, was prepared as early as 1827 Nevertheless, it is true, that compounds having highly polarized M-C, M-H etc bonds may be easily decomposed in water by protonation In other cases, oxidative addition of or oxygen abstraction from water leads to formation of metal hydroxides or oxides, i.e the redox stability of water may not be sufficient to dissolve without deterioration a compound having a highly reduced metal center Still, there are the procedures for preparation of important compounds (such as e.g ) which call for washing the products with water in order to remove inorganics – these compounds cannot be highly sensitive to water Nowadays we look with other eyes at organometallic compounds the family of which has expanded enormously Some members of this family are soluble in water due to their ionic nature; the legions of anionic carbonylmetallates (e.g ) and cationic bisphosphine Rhchelate complexes (e.g ) just come to mind Others obtain their solubility in water from the well soluble ligands they contain; these can be ionic (sulfonate, carboxylate, phosphonate, ammonium, phosphonium etc derivatives) or neutral, such as the ligands with polyoxyethylene chains or with a modified urotropin structure Chapter One of the most important metal complex catalyzed processes is the hydroformylation of light alkenes In the early years the catalyst was based on cobalt and this brought about an intense research into the chemistry of cobalt carbonyls A key intermediate, is well soluble and stable in water and behaves like a strong acid [1] in aqueous solution: For a decade or so was another acclaimed catalyst for the selective hydrogenation of dienes to monoenes [2] and due to the exclusive solubility of this cobalt complex in water the studies were made either in biphasic systems or in homogeneous aqueous solutions using water soluble substrates, such as salts of sorbic acid (2,4-hexadienoic acid) In the late nineteen-sixties olefin-metal and alkyl-metal complexes were observed in hydrogenation and hydration reactions of olefins and acetylenes with simple Rh(III)- and Ru(II)-chloride salts in aqueous hydrochloric acid [3,4] No significance, however, was attributed to the water-solubility of these catalysts, and a new impetus had to come to trigger research specifically into water soluble organometallic catalysts New incentives came from two major sources, and it is tempting to categorize these as “academic” and “industrial” ones In the early fifties the renaissance of inorganic chemistry brought about the need for water soluble, phosphorus-donor ligands in order to establish correlations between metal complex stability and structure and the characteristics of donor atoms in a given ligand set By that time tertiary phosphines, introduced to organometallic chemistry by F G Mann, were widely recognized as capable of coordinating and stabilizing low oxidation state metal ions in organic solvents For Ahrland, Chatt and co-workers it appeared straightforward to derivatise the well-known and conveniently handled triphenylphosphine by sulfonation in fuming sulfuric acid in order to get the required Pdonor ligand for complexation studies in aqueous solution [5] The monosulfonated derivative, 3-sulfonatophenyldiphenylphosphine, nowadays widely known as TPPMS, was successfully used in complex stability measurements which later led to the categorization of ligands according to their donor atoms (ligands of a and b character and the Ahrland-Chatt triangle, forerunner of the hard and soft characterization) TPPMS was then investigated in extensive details by J Bjerrum who established stability constants of complexes of a dozen of metal ions with this ligand [6] In addition to TPPMS, another water soluble tertiary phosphine, 2hydroxyethyldiethylphosphine (abbreviated that time as dop) was prepared and its complex forming properties studied in Schwarzenbach`s laboratory [7] All this had nothing to with catalysis let alone catalysis with 291 Index Index Terms a- acetamidoacrylic acid a- acetamidocinnamic acid a- benzamidocinnamic acid [(Cp*Ir)2(m-OH)3]+ [{OsCl2(TPPMS)2}2] [{Pt3(CO)6}n]2– [{Rh(m-StBu)(CO)(TPPTS)}2] [{RhCl(COD)}2] [{RhCl(HEXNa)2}2] [{RhCl(NBD)}2] [{RhH(COD)}4] [{RuCl2(benzene)2}2] [{RuCl2(TPPMS)2}2] [{RuCl2(TPPTS)2}2] [{RuClH(TPPMS)2}2] [Co(CO)4]– [Co2(CO)6(TPPTS)2] [Co2(CO)8] [CoCp(CO)2] [CoH(CN)5]3– [CoH(CO)3(TPPTS)] [CoH(CO)4] [Cr(CO)6] [Fe(CO)5] [Ir(?5-C5Me5)(H2O)3]2+ [Ir(COD){P(CH2OH)3}2]Cl [Ir4(CO)12] [IrCl(CO)(PPh3)2], trans [IrCl(CO)(TPPMS)2], trans[IrCl(CO)(TPPTS)2], trans[IrH(CO)(TPPTS)3] [IrH3(PPh3)3] [Mo(CO)6] [MoH(?5-C5H5)(CO)2(PCy3)] [Ni(CN)(CO)3]– [Ni(CN)4]2– [Ni(CO)4] [Ni(TPPTS)3] [NiCl2(DPPE)] [Os(H2)(CO)(DPPP)2]+ [OsH4(TPPMS)3] [Pd(MeCN)4](BF4)2 Links 68 68 68 66 90 271 159 69 180 56 128 118 95 104 245 88 90 179 274 50 179 132 132 88 90 132 60 60 266 266 115 132 98 193 251 193 266 215 60 90 164 103 103 285 70 233 286 100 262 103 272 112 283 138 284 91 119 97 124 103 126 282 271 61 109 266 90 91 272 90 110 284 92 161 195 51 52 98 179 93 106 272 267 This page has been reformatted by Knovel to provide easier navigation 292 Index Terms [Pd(OAc)2] [Pd(PPh3)4] [Pd(QS)2] [Pd(TPPMS)3] [Pd(TPPTS)3] [PdCl2(PPh3)2] [PdCl2(TPPMS)2] [PdCl2(TPPTS)2] [PdCl2] [PdCl3(pyridine)]– [PdH(TPPTS)3]+ [PtH(CO)(PiPr3)2], trans[Rh(?5-C5Me5)(bipy)]2+ [Rh(acac)(CO)2] [Rh(BDPB)(COD)]BF4 [Rh(BPPM)(COD)]BF4 [Rh(COD)2]BF4 [Rh(SULPHOS)(COD)] [Rh2(OAc)4] [Rh6(CO)16] [RhCl(CO)(PPh3)2] [RhCl(CO)(TPPMS)2] [RhCl(PPh3)3] [RhCl(TPPMS)3] [RhH(CO)(PPh3)2] [RhH(CO)(PPh3)3] [RhH(CO)(TPPMS)2] [RhH(CO)(TPPMS)3] [RhH(CO)(TPPTS)2] [RhH(CO)(TPPTS)3] [RhH(CO)2(PPh3)] [RhH(CO)2(TPPMS] [RhH(CO)2(TPPTS)] [RhH(PPh3)4] [Ru(6,6`-Cl2bpy)2(H2O)2](CF3SO3)2 [Ru(CO)2(H2O)6]2+, fac[Ru(H2O)6]2+ [Ru(O2CCF3)(CO)3]+, fac- Links 201 215 222 243 288 115 224 59 211 196 137 192 90 210 287 259 199 135 129 151 79 79 232 53 121 132 115 164 115 52 118 150 150 162 151 162 159 173 150 162 162 105 91 198 237 134 210 216 225 250 211 217 227 259 212 218 229 261 213 219 230 267 202 210 218 223 98 214 199 192 194 192 216 109 218 203 210 231 126 219 253 127 230 257 258 200 220 130 168 173 174 285 214 221 242 270 273 259 87 122 136 197 160 57 250 53 119 63 104 105 61 124 62 126 93 247 97 184 185 157 163 158 171 162 163 164 163 160 184 138 165 155 161 156 162 266 267 163 94 244 135 This page has been reformatted by Knovel to provide easier navigation 293 Index Terms [Ru(OAc)(TPPTS)3] [Ru3(CO)12] [Ru3(CO)9(TPPMS)3] [Ru4-(?6-C6H6)4H6]2+ [RuCl(bipy)(CO)]+ [RuCl2(bipy)2] [RuCl2(DMSO)4] [RuCl2(PPh3)3] [RuCl2(PTA)4] [RuClH(PTA)3] [RuClH(TPPMS)3] [RuClH(TPPTS)3] [RuH(?6-arene)(TPPTS)2]Cl [RuH(PTA)5]+ [RuH2(PPh3)4] [RuH2(PTA)4] [RuH2(TPPMS)4] [RuH2(TPPTS)4] [RuHI(TPPTS)3] [W(CH3CN)(CO)3(TPPMS)2] [W(CO)6] [WH(?5-C5H5)(CO)2(PPh3)] 2-oxo-acids, hydrogenation of 2-propanol, transfer hydrogenation with 5-hydroxymethylfurfural ABS -polymers, hydrogenation of acetophenone, hydrogen transfer reduction of acetophenone, hydrogenation of acetylene, trimerization of alcohols, hydrocarboxylation of aldehydes, hydrogenation of aldehydes, transfer hydrogenation of alkenes, hydration of alkyltin derivatives alkynes, hydration of alkynes, hydrocarboxylation of Alloc allyl alcohol, carbonylation of allyl alcohol, hydroformylation of allylic alkylation aminophosphines aminophosphinic acids aminophosphonic acids amphiphiles AOT Links 88 132 152 59 133 133 59 250 93 53 52 90 92 119 115 93 91 92 88 85 132 97 51 108 203 137 134 260 119 93 54 266 267 268 96 102 109 151 87 232 88 89 90 91 22 35 54 119 93 56 95 105 248 202 92 103 270 228 271 198 225 192 180 223 21 79 79 75 78 167 170 This page has been reformatted by Knovel to provide easier navigation 294 Index Terms Links arenediazonium salts arenes, hydrogenation of aryl iodides, hydrocarboxylation of 213 80 195 Barbier-Grignard reactions 231 258 86 193 109 113 122 122 batophenanthroline benzothiophenes, hydrogenation of benzyl halides, hydrocarboxylation of benzyl halides, hydrodechlorination bicarbonate, hydrogenation of biomembranes biomembranes, hydrogenation of bis[(2-diphenylphosphino)ethyl]amine bovine serum albumin, BSA Brij BSA, bovine serum albumin butenes, hydroformylation of Calixarenes carbohydrate-derived phosphines carbohydrates, hydrogenation of carbon dioxide carbon dioxide, hydrogenation of carbon-carbon bond formation carbonylation of allyl alcohol carbonylation of organic halides carbonylation with [Ni(CN)(CO)3]– carbonylation carboxylated phosphines catalyst degradation cell agglutination CHIRAPHOS chloroethanol chloronitroaromatics, hydrogenation of cinnamaldehyde cinnamaldehyde, hydrogenation of citraconic acid citral CO/H2O, hydrogenation with CO-ethene copolymerization colloids, hydrogenation with concanavalin A controlled radical polymerization counter phase transfer catalysis crotonaldehyde crown ethers CTA+HSO4- 33 74 78 74 156 38 29 96 113 103 209 192 192 191 24 155 246 23 259 99 103 89 103 68 136 250 56 246 249 111 93 58 78 228 83 87 195 126 170 179 286 36 97 25 26 36 37 283 93 88 104 125 This page has been reformatted by Knovel to provide easier navigation 77 295 Index Terms Links CTAB cyanation cyclodextrins cyclopropanation cyclotrimerization of acetylenes 170 266 279 231 274 DDAPS 78 74 174 35 127 237 dehydropeptides, hydrogenation of dendrimers diam-BINAP dihydronicotinamide cofactors dimerization DIOP E-factor enantioselective hydroformylation enantioselective hydrogenation epoxides, hydrogenolysis of ethene-CO copolymerization extraction effects in hydrogenation extraction in hydroformylation Fluorous biphase systems, FBS formate, transfer hydrogenation with formic acid geraniol, hydrogenation of geranylacetone guanidinium-phosphines H/D exchange Heck reactions heterolysis of H2 high temperature water (HTW) higher olefins, hydroformylation of homolysis of H2 host-guest interaction HAS, humane serum albumin H-transfer reductions humane serum albumin, HAS hydration of alkenes hydration of alkynes hydration of nitriles hydration hydridoruthenium clusters hydrocarboxylation of 5hydroxymethylfurfural hydrocarboxylation of alcohols hydrocarboxylation of alkynes 95 153 166 69 112 250 105 176 102 11 74 233 22 74 210 48 274 156 48 279 173 103 173 270 271 272 266 82 103 104 105 24 35 219 265 269 106 285 270 203 202 198 This page has been reformatted by Knovel to provide easier navigation 296 Index Terms hydrocarboxylation of aryl iodides hydrocarboxylation of benzyl halides hydrocarboxylation of N-allylacetamide hydrocarboxylation of olefins hydrocarboxylation of phenethyl bromide hydrocarboxylation of styrene hydrocyanation hydrodechlorination hydroformylation of butenes hydroformylation of higher olefins hydroformylation of methyl acetate hydroformylation of N-allylacetamide hydroformylation of styrene hydroformylation hydroformylation, mechanism of hydrogen transfer reduction of acetophenone hydrogen transfer reduction of ketones hydrogenation of 2-oxo-acids hydrogenation of acetophenone hydrogenation of aldehydes hydrogenation of arenes hydrogenation of benzothiophenes hydrogenation of bicarbonate hydrogenation of biomembranes hydrogenation of carbohydrates hydrogenation of carbon dioxide hydrogenation of chloronitroaromatics hydrogenation of cinnamaldehyde hydrogenation of dehydropeptides hydrogenation of geraniol hydrogenation of imines hydrogenation of ketones hydrogenation of nitro compounds hydrogenation of olefins hydrogenation of oximes hydrogenation of phospholipids hydrogenation of polymers hydrogenation of quinoline hydrogenation of sorbic acid hydrogenation of unsaturated acids hydrogenation with [CoH(CN)5]3– hydrogenation with CO/H2O hydrogenation with colloids hydrogenation with Ru(II)-salts hydrogenation hydrogenation, effect of amphiphiles hydrogenation, effect of pH Links 195 193 205 198 195 200 266 109 156 156 181 182 158 149 162 95 94 51 105 92 80 86 113 122 96 103 99 89 74 74 98 232 51 49 51 123 56 86 52 62 50 136 56 49 47 76 92 195 137 179 285 284 87 232 83 87 88 89 99 100 101 98 53 136 59 90 97 283 93 87 282 125 120 This page has been reformatted by Knovel to provide easier navigation 91 297 Index Terms Links hydrogenation, enantioselective hydrogenation, mechanisms of hydrogenolysis of epoxides hydrogenolysis of organic halides hydrogenolysis hydrophosphination hydroxypalladation hydroxyphosphines 69 58 112 109 109 273 230 25 Ibuprofen 204 98 111 97 85 266 74 68 265 103 ketones, hydrogenation of Kuraray 94 232 180 240 Liposomes 123 M acroligands 27 173 122 18 103 181 260 171 172 217 260 260 233 28 29 30 19 74 223 86 128 127 111 205 182 204 274 272 252 imines, hydrogenation of inverse phase transfer catalysis ionic hydrogenation ion-pairs isomerization isotope exchange, H/D itaconic acid Ketones, hydrogen transfer reduction of membranes, biological MeOBIPHEP mesaconic acid methyl acetate, hydroformylation of methylmorpholine oxide micelles microemulsions microwave irradiation MMO Mukaiyama oxidations myrcene Na2DPPPDS NAD(P)H NADH NaH2PO2, transfer hydrogenation with N-allylacetamide, hydrocarboxylation of N-allylacetamide, hydroformylation of Naproxen near-critical water nitriles, hydration of 27 99 100 101 93 269 31 This page has been reformatted by Knovel to provide easier navigation 66 298 Index Terms nitro compounds, hydrogenation of Olefins, hydrocarboxylation of olefins, hydrogenation of oligomerization Oppenauer oxidation organic halides, carbonylation of organic halides, hydrogenolysis of oxidation with Pd/batophenanthroline oxidation oximes, hydrogenation of PEG pH, effect on hydroformylation pH, effect on hydrogenation of aldehydes pH, effect on hydrogenation of bicarbonate phase transfer phenethyl bromide, hydrocarboxylation of phenylacetylenes, trimerization of phospholipids, hydrogenation of phosphonato-phosphines phosphonium phosphines phosphonium salts poly(ethylene oxide)phosphines poly(phenylene oxide), PPO polymerization polymers, hydrogenation of promoter ligands propynoic acid, trimerization of protecting groups, removal of protein ligands PTA quinoline, hydrogenation of Reductive amination Rh-thiolato complexes rigid rod polymers ROMP Ru(II)-salts, hydrogenation with Ru-arene complexes Ruhrchemie-Rhône Poulenc process Salt effects SAPC SDS SHOP SKEWPHOS solubility Links 51 198 49 237 262 192 109 258 258 51 11 164 92 120 195 247 123 34 32 64 175 249 237 56 184 247 225 74 11 86 51 159 218 243 49 80 88 71 23 153 98 136 53 59 67 158 58 105 55 54 240 161 268 174 23 87 111 53 133 81 152 82 83 78 170 224 281 160 84 This page has been reformatted by Knovel to provide easier navigation 299 Index Terms Links solubility of hydrogen solubility of n-alkenes solubility of phosphines solvation solvofobicity parameter, Sp Sonogashira coupling sorbic acid, hydrogenation of spectator ions Stille coupling styrene, hydrocarboxylation of styrene, hydroformylation of sulfonated phosphines SULPHOS (31) supercritical CO2 supercritical water surfactants Suzuki coupling 48 154 39 101 73 209 52 163 209 200 158 14 53 5 76 209 T EDICYP 223 242 242 telomerization of butadiene with ammonia telomerization of butadiene with sucrose telomerization of butadiene with water telomerization tiglic acid tin, alkyl derivatives TPPDS TPPMS TPPTS transfer hydrogenation of aldehydes transfer hydrogenation of unsaturated acids transfer hydrogenation with 2-propanol transfer hydrogenation with formate transfer hydrogenation with NaH2PO2 transfer hydrogenation trimerization of acetylene trimerization of phenylacetylenes trimerization of propynoic acid trimerization tris(hydroxymethyl)phosphine Tsuji-Trost coupling Tween 20 Unsaturated acids, hydrogenation of 240 239 103 228 14 14 14 103 218 249 227 15 86 275 274 167 214 16 160 17 18 105 106 170 229 53 103 108 102 111 102 248 247 247 247 242 209 78 62 103 104 284 221 170 282 unsaturated acids, transfer This page has been reformatted by Knovel to provide easier navigation 300 Index Terms Links hydrogenation of 103 Valeraldehydes 179 Wacker oxidation 257 131 131 287 161 161 18 200 36 water gas shift reaction WGSR XANTHPHOS Zeise`s salt 157 169 182 This page has been reformatted by Knovel to provide easier navigation 183 Index 301 KEY TO THE ABBREVIATIONS acacH Aliquat 336 Alizarin red amphos AOC AOT BDPB BDPP BDPPTS BIFAPS BINAP BINAS BIPHLOPHOS bipy BISBIS BPPM Brij BSA Bu CBDTS CD CHIRAPHOS Cn COD Cp Cp* CTAB DBA DDAPS diam-BINAP DIOP DMF = 2,4-pentanedione (acetylacetone) = trioctylmethylammonium chloride = sodium 1,2-dihydroxy-9,10-anthraquinone-3sulfonate = 2-diphenylphosphinoethylammonium ion = aqueous organometallic catalysis = see p.78 = 1,4-bis(diphenylphosphino)butane = 3-benzyl(p-sulfonate)-2,4-bis(diphenylphosphino)pentane = 2,4-bis(diphenylphosphino)pentane = tetrasulfonated BDPP = 50, see p 18 = 2,2’ -bis(diphenylphosphino)-1,1’ -binaphtyl = 52, see p 18 = 43, see p 18 = 2,2’-bipyridine = 46, see p 18 = (2S,4S)-N-t-butoxycarbonyl-4-diphenylphosphino-2(diphenylphosphinomethyl)pyrrolidine = see p.78 = bovine serum albumin = butyl = tetrasulfonated cyclobutane-DIOP, 37, see p 17 = cyclodextrin = 2,3-bis(diphenylphosphino)butane = 1,4,7-trimethyl-1,4,7-triazacyclononane = 1,5-cyclooctadiene = hexadecyltrimethylammonium bromide = 1,5-diphenyl-1,4,-pentadiene-3-one (dibenzylideneacetone) = see p.78 = 160, see p.35 = trans-4,5-bis(diphenylphosphinomethyl)-2,2dimethyl-1,3-dioxolan = dimethylformamide Index DMSO DOPC DPPC DPPE DPPP DPUP EDTA Et FBS HSA HLB hm-pybox 302 = = = = = dimethylsulfoxide dioleoylphosphatidylcholine dipalmitoylphosphatidylcholine 1,2-bis(diphenylphosphino)ethane 1,3-bis(diphenylphosphino)propane = ethylenediaminetetraacetic acid = ethyl = fluorous biphase systems = humane serum albumin = hydrophilic-lipophilic-balance = see p 232 = isopropyl = methyl Me = 182, see p 36 NADH = nicotinamide adenine dinucleotide NBD = bicyclo[2.2.1]hepta-2,5-diene (norbornadiene) NORBOP = 96, see p.26 PAA = poly(acrylic acid) = tricyclohexylphosphine = poly(ethylene glycol) PEG = poly(ethylene oxide) PEO = phenyl Ph phophos = 159, see p 34 = triphenylphosphine PPO = poly(phenylene oxide) Pr = propyl PTA = 1,3,5-triaza-7-phosphaadamantane PVP = poly(N-vinylpyrrolidone) SAPC = supported aqueous phase catalysis SDS = sodium dodecylsulfonate SKEWPHOS, see BDPP Span 40 = sorbitan monopalmitate SULPHOS = 31, see p 15 TEDICYP = cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane TfOH = trifluoromethylsulfonic acid THF = tetrahydrofuran TPPDS = disulfonated triphenylphosphine, 2, see p 14 TPPMS = monosulfonated triphenylphosphine, 1, see p 14 TPPTS = trisulfonated triphenylphosphine, 3, see p 14 Triton X-100 = see p 224 Index 303 Tween = see p 78 = water gas shift reaction WGSR XANTHPHOS, sulfonated = 48, see p 18 Catalysis by Metal Complexes Series Editors: R Ugo, University of Milan, Milan, Italy B R James, University of British Columbia, Vancouver, Canada 1* F J McQuillin: Homogeneous Hydrogenation in Organic Chemistry 1976 ISBN 90-277-0646-8 P M Henry: Palladium Catalyzed Oxidation of Hydrocarbons 1980 ISBN 90-277-0986-6 R A Sheldon: Chemicals from Synthesis Gas Catalytic Reactions of CO and 1983 W Keim (ed.): Catalysis in ISBN 90-277-1489-4 Chemistry 1983 ISBN 90-277-1527-0 A E Shilov: Activation of Saturated Hydrocarbons by Transition Metal Complexes 1984 ISBN 90-277-1628-5 F R Hartley: Supported Metal Complexes A New Generation of Catalysts 1985 ISBN 90-277-1855-5 Y Iwasawa (ed.): Tailored Metal Catalysts 1986 G Strukul (ed.): Catalytic Oxidations with Hydrogen Peroxide as Oxidant 1993 ISBN 0-7923-1771-8 ISBN 90-277-1866-0 R S Dickson: Homogeneous Catalysis with Compounds of Rhodium and Iridium 1985 ISBN 90-277-1880-6 10 A Mortreux and F Petit (eds.): Industrial Applications of Homogeneous Catalysis 1988 11 ISBN 90-277-2520-9 N Farrell: Transition Metal Complexes as Drugs and Chemotherapeutic Agents 1989 ISBN 90-277-2828-3 12 A F Noels, M Graziani and A J Hubert (eds.): Metal Promoted Selectivity in Organic Synthesis 1991 13 ISBN 0-7923-1184-1 L I Simándi: Catalytic Activation of Dioxygen by Metal Complexes 1992 ISBN 0-7923-1896-X 14 K Kalyanasundaram and M Grätzel (eds.), Photosensitization and Photocata- 15 lysis Using Inorganic and Organometallic Compounds 1993 ISBN 0-7923-2261-4 P A Chaloner, M A Esteruelas, F Joó and L A Oro: Homogeneous Hydrogenation 1994 ISBN 0-7923-2474-9 Catalysis by Metal Complexes 16 G Braca (ed.): Oxygenates by Homologation or CO Hydrogenation with Metal Complexes 1994 ISBN 0-7923-2628-8 17 F Montanari and L Casella (eds.): Metalloporphyrins Catalyzed Oxidations 1994 ISBN 0-7923-2657-1 18 P.W.N.M van Leeuwen, K Morokuma and J.H van Lenthe (eds.): Theoretical Aspects of Homogeneous Catalysis Applications of Ab Initio Molecular Orbital Theory 1995 ISBN 0-7923-3107-9 19 T Funabiki (ed.): Oxygenases and Model Systems 1997 20 S Cenini and F Ragaini: Catalytic Reductive Carbonylation of Organic Nitro ISBN 0-7923-4307-7 Compounds 1997 21 A.E Shilov and G.P Shul’pin: Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes 2000 ISBN 0-7923-6101-6 22 P.W.N.M van Leeuwen and C Claver (eds.): Rhodium Catalyzed Hydroformylation 2000 ISBN 0-7923-6551 -8 23 F Joó: Aqueous Organometallic Catalysis 2001 ISBN 0-7923-4240-2 ISBN 1-4020-0195-9 KLUWER ACADEMIC PUBLISHERS – DORDRECHT / BOSTON / LONDON *Volume is previously published under the Series Title: Homogeneous Catalysis in Organic and Inorganic Chemistry ... look at the history of aqueous organometallic catalysis 1.2 General characteristics of aqueous organometallic catalysis References Ligands used for aqueous organometallic catalysis 2.1 Tertiary... reactions in aqueous media 9.1 Aqueous organometallic catalysis under traditional conditions 9.2 Emerging techniques References 265 10 Host-guest chemistry in aqueous organometallic catalysis 10.1... General characteristics of aqueous organometallic catalysis In the simplest form of aqueous organometallic catalysis (AOC) the reaction takes place in a homogeneous aqueous solution This requires