INDEX

abstraction-recombination mechanism 275 acetaldehyde

by methanol homologation 106 hydrogenation to ethanol 126 reaction with HCN 219 reductive elimination of 125

acetate formation 130 acetates, formation of in methanol homol­

ogation 126 acetic acid 89

by methanol carbonylation 106 from methanol 97 from methylformate 102

act'lic anhydride 98,99 acetone, reaction with HeN 219 acetonitrile, from ammonia and ml'lhanr

248 acetyl cobalt

complex 125 intermediate in methanol homologation

121 acetyl iodide, hydrolysis of 126

cyclopropcnation of 283 hydrocyanation of 223 production from methane 248

acidic cocatalysts 227 acids, reaction \Iith HeN 231 acrylamidcs 162 acrylates, synthesis of 162 acrylic acid 157 , 162

BASF process 139 from ethylene, mechanism 163 Rohm and Haas process 139 synthesis from acL'tyknc 137

acrylonitrile 219,248 . reaction with HeN 232 syn thesis from acetylene 223 synthesis of 234, 236

activation of C-H bonds, intramolecular 255 of CO, by coordination to palladium 159

of FT catalysts 60 of HCN by cuprous salts 228 of metal centers 151 of methane 251

acyl clusters 21. 22 co.mpkxes 1. 21 , 22,153

as intermediates 140 acyl-metal bond 153 acylium cations 156 adarnantane, chlorination of 257 addition

of carbalkoxycarbc'nes 283 to nitriks 272

of HeN onto butadiene 225 adenine 219, 239

formation, mechanism 239 formation from HeN 224

adiponitrile, synthl'sis from butadiene 224 adsorbed mdhyl, chain initiation by 67 aggregation of iron catalysts 57 alanine 240 alcohol

homologation 136 selectivity, effect of reaction para­

meters on 68 alcohols

from FT synthesis 42 homologation of 105 secondary reactions in FT synthesis 56 selective formation by homologation

105 syntht'sis from alkent's 136

aldehyde intermediates 26 aldehydes

formational' 291 selective formation by homologation

105 synthesis from alkenes 136

aldol condensation 108 alkali cyanides 222

295

296 INDEX

alkane activation 252 carbenes as intermediates 263

alkanes activation

by metal complexes 255 by metal ions 256 by metallo enzymes 257 on metal surfaces 255

chlorination by CCl. 257 cobalt acetate oxidation 256 hydrogenolysis of 285 isomerization of 255 , 286

alkene carbonylation 140 alkcnes, reaction with CO, 191 alkyl formatcs, synthesis from CO, 186 alkylation of CO 11 alkylcarbonatc complexes 178 alkylcopper complexes 171 alkylidene

carbene rearrangement 289 carbenoids 289 complexes 284

alkyltitanocene, reaction with CO 2 173 alkyne carbonylation 137 alkyncs, reaction with CO, 189 allene

reaction with CO, 191 synthesis of 276

allyl intermediates 227 nickel compounds 173 palladium catalysis 282 thioethers 274 titanium complexes, reaction with CO,

173 ambiphilic carbencs 267 amino acids 240

preparation of 235 aminomalonitrile 239 ammonia, formation from methane 250 ammonoxidation 220

of methanol 220 Anderson-Emmett 23

mechanism 78 Ando, W. 273 Andrusso\\' process 247 anodic oxidation of cyanides 230 Aratani 279 Aresta 170

ARGE high load fixed bed process 44, 45 process 68 product distribution 46

Arndt-Eistert synthesis 277 aromatics

ring enlargement of 271 synthesis from methanol 94 , 96

arsines as ligands 114 Ashworth, T. V. 180 aspartic acid 240 asymmetric copper catalysts 279 Auger spectroscopy 64 aziridines, reaction with CO, 198 azulinic acid 240

Bahrmann mechanism 123 BASF process

production of propionic acid 141 synthesis of HCN 220

benzylalcohol, homologation of 120, 121 Berty, J. 107 bicarbonate complexes 178 bimetallic catalysts 107

complexes 34,92 oxymethylene bridged species 80

binuclear Pt complexes, formation of 255 biological oxidation of methane 251 biomimetic reactions 257 bipyridyl, formation of 237 biscarbonylation of acetylene 138 Blyholder, G. 67 bonding energies

for CO to transition metals 55 for H, to transition metals 55

Boudouard reaction 50 bridge methylene ligands 287 bromine compounds, as catalyst poisons 59 Buchner synthesis 275 butadiene

hydrocyanation of 224, 229 reaction with CO 2 192

butadiene oxides, reaction with CO 2 196 butanol

formation in methanol homologation 108

synthesis from CO, 184 butencdiol , reaction "ith HCN 230 butyraldehyde, formation in methanol

homologation 108

INDEX 297

butyric esters, synthesis from CO 2 191

C-13 carbided surface 65 C-14 labelled ketene 67 C--C-bond formation 19 C-H insertion reactions 267 C, --C. alcohols from CO 75 C-14 labelled methanol, homologation of

122 C2 --C. olefins 58, 69 carbalkoxycarbenes 264,275,283

addition to nitriJes 272,277 insertion into C-H bonds 283

carbamate complexes 180 carbene

as intermediate in methanol homologa-tion 122

complexes as intermediates 15, 19, 28 of tungsten 285 mechanism 122 metal complexes 268 rearrangements 277 species, in FT synthesis 75

carbene-metal bond, nature of 285 carbenes 95,263

by elimination reactions 271 in fine-chemical synthesis 271 in Fischer-Tropsch reactions 287 cycloaddition of 272

reactions of 268 to alkynes 273 to olefins and acetylenes 271

generation by elimination reactions 267 from diazo compounds 267

generation of 267 hydrogenation of 290 insertion of 273,283

into X-H bonds 271 reactions 268,283

with methane 250 reactivity of 264 regioseiectivity of 266 selectivity index 273 spin states of 267 structure of 263

carbenoid mechanism 252,281 carbenoids 253,268

formation by elimination of a methoxy group 270

by migration of hydrogen 270 in fine chemical synthesis 278 in industrial processes 283 nucleophilic character 289 spectra of 269 structure of 269

carbide clusters 23 complexes as intermediates 15,24 formation 57 hydrogenation 271,287 mechanism 75 phases 62

carbidic intermediates 65 iron clusters 69 species, in FT synthesis 75

carbodiimides 203,283 carbon deposition 57

in FT syn thesis 47 effect of reaction parameters on 68

carbon deposits, hydrogenation of 63 carbon dioxide, see CO 2

carriers, reversible 171, 196 catalytic reactions 183 chemical utilization 169 reactions with hydrogen 183 reserves of 169 stoichiometric reactions 170

carbon disulfide 247 carbon monoxide, see CO

hydrogenation, see reduction insertion 151 reduction

ca taly tic 26 model reactions 5 stoichiometric 5

carbonaceous deposits, in FT synthesis 46

carbonates 157 cyclic 195 monomeric 195 synthesis of 165

carbonic anhydrase 171 , 178 carbonyl species from CO insertion, in FT

synthesis 75 carbonylation, see CO insertion

in acidic conditions 155 of alkenes 140

298 INDEX

carbonylation (continued) of alkynes 137 of unsaturated organic substrates 135 reactions 135 under oxidative conditions 156

carboxy1a1koxy palladium complexes 160 carboxylate complexes 170, 190, 193 carboxyla tion

of epoxides 197 ofdhylene 191 of methane 249

carboxylic acids 192 carbyne complexes 16 Casey, C. P. 285 catalyst

deactivation 59 by carbon deposition 59 in hydrocyanation reactions 228

dispersion 69 metals , for FT synthesis 42,55 recycling, in methanol homologation

108 supports, effect on selectivity 69

ca talysts for metathesis reactions 284 for FT synthesis 55 highly dispersed, on AI,O, supports 57

catalytic cycle for cobalt-catalyzed hydroformylation 143

of Reppe-type reactions 154 catalytically active sites 69 Caulton, K. G. 289 chain

branching, effect of reaction parameters on 68

growth in Fischer-Tropsch reaction 290 initiation 76

by adsorbed methyl species 67 length, effect of reaction parameters on

68 propagation

by CO 67 by insertion of methylene groups 67 in CO hydrogenation 53 in FT synthesis 75

start , in FT synthesis 75 termination

in CO hydrogenation 53 in FT synthesis 75

chelating ligands in methanol homologa-tion 115

chemical trapping of residual species 81 Chisholm, M. H. 178 chlorination

of adamantane 257 alkanes by CCl4 257 of methylpcntane 257

chlorine compounds, as catalyst pOl SO\lS 59

chloromethanes 246 chromium amides 182 chromium hydride complexes 177 chrysanthemates 280 CHx as intermediates in methanation 65 clusters 8,32,35

fragmentation III homologation catalysts III hydroformylation catalysts 110 in methanol homologation 116 with acyl ligands 21, 22 with CO 8 with methoxy ligands 9

CO see also carbon monoxide activation of 6-8

on catalyst surface 64 via carbcnes 15 via carbides 15 via formyl complexes 12, 30 via hydroxy methyl 14 via hydroxymdhylene 14

alkylation of 11 bonding 7

energies to transition metals 55 chemisorption 7, 92 clusters 8 complexes 6 coordination of 6, 8, 12 coordination to palladium(lI) ions 159 dissocia tion 8, 91

on iron surfaces 59 dissociative adsorption 64,68, 75, 82 elcctrophilic attack on 10 from ethanol 97 heat from adsorption 56 hydrogenation 270

kinetics 74 over alkalized iron catalysts 43

INDEX 299

CO (continued) hydrogenation (continued)

over nickel 43 over rhodium 74

insertion 14,19,20,23,25,80,91,99, 121,125

into ruthenium methyl bond 130 IR frequ encies 7 molecularly adsorbed 65 nucleophilic attack on 10, 13, 29 oligomerization, growth 6.25 partial pressure, influence in hydro­

formylation 144 protonation of 11, 18, 27 reduction

by hydrogen 12, 29 homogeneous 29

by metal hydrides 12 to methanol, mechanism 90

reductive oligomerization of 42 scission 8 sdectivc synthesis of alcohols from 72 side-on molecular coordinated 82

CO/H , chemisorption 55 heterogeneous conversion

catalysts 43 reaction conditions 43

physisorption 55 CO 2 , see also carbon dioxide

as by-product in methanol homologa-tion 128

as homologation by-product 105 chemical utilization of 169 cobalt complex of 170 co catalyst

in dimerization reactions 205 in homogeneous catalysis 205 in hydroformylation 207 in metathesis 206 in polymerization 207 in telomerization reactions 206

deoxygenation of 199 dimerization of 203 disproportionation of 199 formation in methanol homologation

108 from mcthanol 96 hydrogenation to methane 51 insertion

into M-C bonds 170 into M -H bonds 175 into M-N bonds 180 into M-O bonds 178

nickel complexes of 170 niobium complex of 170 reaction with

alkenes 191 alky1copper complexes 171 allene 191 azirid ines 198 butadiene 192 copper complexes 176 dicncs 191 epoxides 188 ethylenciminc 199 iridium complexes 174 isoprene 194 methylenecycJopropanes 194 organozinc compounds 171 propyleneiminc 199 strained heterocycles 195 titanium complexes 173 viny1coppcr complexes 171 zirconium complexes 176

reactions with alkynes 189 hydrocarbons 189

reduction of 199 CO(CO)4

nucleophilic attack of 121 reaction with methyl iodide 124

Co, (CO). 109 disproportionation of 110, 121

coal conversion to liq uid hydrocarbons 41 world production 41

coal gasification, production of methan e 246

cobalt acetate oxidation of alkanes 256 carbenoids 278 carbon dioxide complex 170 carbonyl catalysts

phosphine-modified 145 unmodified 142

carbonyl complexes, in hydroformyla­tion 141

carbonyl phosphine complexes carbonyls on Y zeolites 70

142

300 INDEX

cobalt (continued) catalysts (continued)

active metal surface area 56 alkali promoters 56 for FT synthesis 42,55 for normal pressure FT synthesis

44 thorium promoters 56 unpromoted, for methanol homol-

ogation 109,110 catalyzed methanol homologation 107 clusters, zeolite entrapped 72 complexes 34

one component catalysts for homol­ogation III

[(;action with CO 2 201 homologation catalyst 105 hydride complexes 177 intermediates. coordinated by phosph·

ines 124 cobalt/iodine Cil talysts 107 cobalt/ligand/iodine complexes III cobalt/ruthenium catalysts 107

for homologation 115 cocatalysts 227 cometals as hydrogenation catalysts in

homologation 115 commercial FT plant 48 competition measurements 269 cumplexes of cobalt 34 condensa tion of surface hydroxycarbene

78 conjugated dienes, reaction with cyanogen

237 continuous gas phase processes for methanol

homologation 117 coordination

of CO, see CO coordination uf formaldehyde 15 of HCN 222

coordinative mechanism 281 copper

alkoxides 158, 178 amides 180 benzophenone 259 carbenoids, regioseiectivity of 280 catalysis 225,278 catalysts in the synthesis of carbonates

165

catalyzed carbene reactions, mechanisms 280 halogenation 224 hydrocyanation 223,228

complexes, reaction with CO 2 171 cyanides 228 cyanoacetatc 196 hydride complexes, reaction with CO,

176 trinate 281,283

coupling of alkoxycarbonyl moieties 161 of allyl groups 162

crotonaldehyde, formation in methanol homologation 108

crown ether catalysis 233 CS 2 formation 249 cupric methoxychloride, reduction by CO

165 cuprous salts, activation of HCN 228 cyanamide 219,220,241 cyanobutadicne 230 cyanogen 219

addition of HCN 237 chemistry 236 reaction

with dienc, 237 with hydrocarbons 231 with vinyl aluminate 236

cyanogen chloride 219 addition to acetylene 223 cyclotrimerization of 238

cyanohydrins as cyanation reagents 233 formation of 234

cyanopyridines, formation of 237 cyanosilylation 234 cyanuric chloride 219,238 cycioaddition 265

of carbenes 272 of carbcnes to alkynes 273 of carbenes to olefins 271 reactions of carbenes 268

cycloheptatrienes 275 cyclohexane, photochemical dehydrogena-

tion 258 cyclohexenc oxide, reaction with CO 2 198

cyclopropanation 283 cyclopropane derivatives 272

INDEX 301

cyclopropanes asymmetric synthesis of 278 formation of 271

cyc1opropenation of acetylenes 283 cyclopropenes

formation of 271 synthesis of 273

cyclopropenyl carbenes 276 cyclotrimerization

of cyanogen chloride 238 of HCN 238

Darensbourg, D. J. 177 deactivation of iron catalysts by sulfur

59 decarbonylation 13 decomposition of diazo compounds 267

photochemical 268 thermal 268

Dcgussa process, synthesis of HCN 220, 247 dehydrogenation of cyclohexane 258 Deluzarche mechanism 81 deoxygenation

copper-promoted 203 of CO, 199

by phosphines 202 determination of product distribution 54 diaminomaleonitrile 219,237,239 diarylcarbenes, reaction with cyclopenta-

diene 267 diazo compounds

photochemical decomposition 268 thermal decomposition 268

diazomethane, reaction over metals 67 diazomethane/H" reaction over metals 67,

77 dibromocarbenes, reaction with acetylenes

276 dichlorobutenes 224

isomerization of 224 dichlorocarbene 272,275

generation from chlorl rm 267 dicyanobutene 224,230 dicyanoimidazole 239 dienes

hydrocyanation of 229 reaction with CO, 191 reaction with cyanogen 237

diesel oil, FT synthesis 49

diethyl ketomalonate 203 dihydroxypyrimidines 239 diiminosuccinonitrile 219

formation of 237 dimerization

of butadiene 205 of CO, 203 of isoprene 206 of oxycarbenes 290 of transition metal bonded carbenes 289

dimethyl carbonate 165 dimethyl formamide 241 dimethylamine 241 dimethylether, formation in methanol homo­

logation 108 dimethylformamide, synthesis from CO,

187 dimethylmaleate, from acetylene 138 dinuc1ear carbene complexes of tungsten

285 dinuclear clusters 287 diphenyl titanocene, reaction with CO,

173 diphenylcarbene 275 diphenylketene 203 disproportionation of CO, 199 dissociation of CO 91 dissociative adsorption of CO 64 double CO insertion 22 Du Pont process, synthesis of adiponitrile

224,225 dual product distribution 54 dyes 238

early transition metals oxophilic character 82 promoters for olefin formation 71

Eckstrom-Adock carbide 62 electolytic processes 239 elimination reactions of halogen com-

pounds 267 English, A. D. 174 enolic complexes chemisorbed on iron 79 entrained bed process 44 entrained fluidized bed reactors 46 enzymatic oxidation of methane 251 epichlorohydrin, reaction with CO, 196 epoxide carboxylation 197 epoxides, reaction with CO, 195

302 INDEX

esters 191 , 192 ethanol

by hydrogenation of acetaldehyde 126 by methanol homologa tion 106 from CO, kinetics 74 incorporation into FT products 66 synthesis

from CO 73 from CO 2 184 over supported rhodium catalysts 74

ethoxy cobalt intermediate 126 ethoxy ruthenium intermediate 130 ethylene

carboxylation of 191 incorporated in FT products 66 metathesis in FT synthesis 55 oxycyanation of 230 via methanol homologa tion 106

ethylene glycol 32,98,100,102 by reduction of oxalates 157 homologation of 121 synthesis 290

ethylene oxide , reaction with CO, 196 ethylenediamine, synthesis of 236 ethyleneimine, reaction with CO, 199

fertilizer 238 Fischer, F. 240 Fischer carbcnoids, spectra of 269 Fischer complexes 269 Fischer-Tropsch 6, 23 91

mechanism 75 reaction, mechanism of 270, 287,290 synthesis, see also FT synthesis 41, 263

fixed bed reactors for FT synthesis 44 , 45 plugging of in FT synthesis 46

fixed fluidized bed process 47 fluidized bed reactors 44 , 46 t1uorochloromethanes 247 Flynn, B. R. 180 formaldehyd e 15, 183

by oxidation of methane 98 complexes 15, 26, 35 coordination of 248 oxygen coordinated 82 reductive dimcrization of 290

formam ide dehydration 220 formamides, synthesis 241

from CO , 187 formate complexes 175,185 formation enthalpies for hydrocarbons from

CO/H, 50 formation

of C-C-bonds 19 of metal-carbon bonds 151

formic acid salts 186 synthesis from CO 2 184, 203

formyl complexes as intermediates 12 intermediates 91 ligands, reduction of 81 species 290

free enthalpies, effect of temperature on, in FT syn thesis 52

FT catalysts activation 60 alterations under synthesis conditions

62 copper promoters 60 C, -C 4 olefins from 49 poisons 59 preparation 59 reduction 60 supports 58

FT commercial processes, product distribu­tion 46

FT evaluation of proposed mechanisms 82 FT iron catalysts

deactivation of by carbon deposits 63 effect of operational period 63

FT reaction mechanisms 75 FT synthesis

ARGE high-load fixed bed process 45 basic features 49 ca talyst metals 42 catalysts 55 dual product distribution 54 fuel cells 93 historic developments 43 linear alcohols from 49 linear olefins from 49 molecular weight distribution 52 polymethylene from 49 probability of product formation 51 product distribution with iron catalysts

53

INDEX 303

FT synthesis (continued) product selectivity control 68 product separation 42,49 production plants 41,44,48 selectivity limitation 54 stoichiometry 50 tailoring of product distribution 55 technical realization 45 thermodynamics 51 \\"axes from 49

functionalizcd olefins, hydrocyanation of 231

fused iron catalysts 57,61 fused iron catalysts, treatment with NH3

73

gasoline, from FT synthesis 49 Gassman 285 genera tion of carbenes 267 geometric progression coefficient 53 geometric restrictions 58, 69 glycine 240

preparation of 235 Green, M. L. H. 284 Group V triphenyl derivatives as ligands

114 growth of hydrocarbon chains, on ruthe-

nium 65 gro,,·th products 19,26 guanine 239 Guczi, L. 256

H-D exchange 252,263 H" bonding energies to transition metals

55 heat of adsorption 56

hafnium amides 181 halogenation of methane 246 Hammett parameters 272 hard wax, from FT synthesis 49 Haynes, P. 187 HCN, see also hydrocyanation

acidic hydrolysis of 239 application of 219 coordination modes of 221 cyclotrimerization of 238 destruction of 241 future applications 220 hydrogenation of 241

hydrolysis of 241 oligomers of 219 oxidation of 241 oxidative addition of 222 physiological properties 241 polymerization of 239 preparation of 220 production of 247 properties of 221 protection equipment 242 reaction with butenediol 230 reaction with multiple bonds 223 synthesis from CO and NH3 221 tetramerization of 239 toxicity of 221, 242

HCo(CO)4 34,110,120,121,126 head-to-head connection 204 head-to-tail connection 204 Hecht, O. 120 Henrici-Olive and Olive mechanism 81 Herskovitz, T. 174 heterocycles, reaction with CO, 195 heterogeneous catalysts for methanol homol-

ogation 117 heterogeneous hydrogenation catalysts in

homologation 116 high-pressure reduction, see reduction Hogeveen, H. 254 homogeneous bimetallic catalysts in homol­

ogation 116 homologation

alcohols 136 relative reaction rates 121

benzylalcohols 120, 121 C-14-labelled methanol 122 CO, as by-product 105 catalyst metals 120 ethanol 121 ethylene glycol 121 general definition 105 H,O as by-product 105 isopropanol 121 methanol 98,105 p-methoxybenzyl alcohol 121 p-substituted benzyl alcohols 120 perdcuterated methanol 122 primary alcohols 120 secondary alcohols I 20 side products 106

304 INDEX

homologation (continued) t-butanol 121, 122 tertiary alcohols 120

HSAB theory 274 hydantoin intermediates 235 hydride-tran sfer 93 hydridocobalt carbonyl 143 hydridorhodium carbonyl complexes 14 7 hydrindane type poly cycles 233 hydrocarbon

activation 285 from methane 250 hydrogenolysis of 255

hydrocyanation see also HCN acetylene 223 C-N bonds 234 C-O bonds 234 catalyst deactivation 228 copper catalysis, mechanism of 228 conjugated dienes 227 dienes 229 functionalized olefins 231 inhibition of 228 mechanism of 226 octatricne 229 olefins 223 regioselectivity of 226 selectivity of 226 under heterogeneous conditions 230 unsaturated hydrocarbons 223

hydrocyanic acid, production of 247 hydroformylation 135, 136, 141, 207

activity of transition metals 142 associative catalysis cycle 149 catalysts 141 dissociative catalysis cycle 148 processes, operating data 142 reaction 79 se lecti vi ty 144

hydrogen from methanol 96 iodide as promotl'r 112 migra tion 270 oxidative addition of 125,151 production 245

hydrogen-deuterium exchange in methane 285 of alkanes 255

hydrogenation aldehydes, cobalt-catalyzed 145 carbenes 290 carbides 271 catalysts for acetaldehyde 126 catalysts in methanol homologation 115 CO, 183 coordinated CO 270 HCN 241

hydrogenolysis of alkanes 285 hydrolysis ofHCN 239,241 hydroxy complexes 185 hydroxy methylidyne complexes 14 hydroxy oxazinones 198 hydroxy oxazolidinones 198 hydroxycarbene mechanism 78

modified 79 hydroxycarbenes 290

by hydrogenation of CO 270 hydroxyethyl cobalt intermediate 126 hydroxyl radicals 257 hydroxylation activity of enzymes 257 hydroxymethyl complexes 14 hydroxymethylene complexes 14, 15, 91 hydroxyuracil 239 hypoxanthine 239 Hiigg carbide FesC, 62

imidazolcs 219,240 imido compounds, reaction with CO, 182 imines

reaction with CO, 195 reaction with HCN 234

iminoacetonitrile 239 iminoacetonitrile 235 in-situ IR spectroscop y, in FT synthesis

64 induction of chirality 282 Inoue, S. insertion, see also CO insertion

carbalkoxycarbenes 283 into C-H bonds 283

carbenes 273 into C-H bonds 274 into N-H bonds 283 into O-H bonds 283 into S-H bonds 283 into X-H bonds 271

carbon dioxide 170 CO 91 , 99,151

INDEX 305

insertion (continued) CO (continued)

double 22 into Pd-C bonds 160

CO, into M--C bonds 170 into M-H bonds 175 into M-N bonds 180 into M-O bonds 178

methylene groups 67,76 reactions of carbenes 268

intermediate acetyl, cobalt 125 CHx ' in methanation 65 ethoxy cobalt 126 ethoxy ruthenium 130 hydroxyethyl cobalt 126 methyl cobalt 125 methyl iron carbonyl 129 ruthenium acetyl 130 ruthenium methyl 130 surface formyl 65 surface hydroxycarbene 65

iodides, ionic, as promoters 112 iodine

as promoter 112 compounds as promoters in methanol

homologation 112 oxidative addition of 125

for ruthenium catalysts 129 role of, in methanol homologation

123 reductive elimination of 125

iodine/cobalt ratio, effect in methanol homologation 112, 113

IR measurements of CO adsorption on nickel 65 under homologation conditions 110

iridium catalysts for methanol homologation 127 complexes, reaction with CO, 174 hydroxy complexes 180

iron, homologation catalysts 105 iron carbide clusters, as model compounds

66 iron carbonitride 73 iron carbonyls

impregnation of AI, 0 3 with 69 on Y zeolites 71

iron catalysts alkali promoters 56 copper promoters 56 electronic promoters 56 for FT synthesis 42,55 for methanol homologation 127 methods of preparation 61 nitridation 57 nitrided 73 potassium promoters 56 properties 61 structural promoters 57 surface area 57

iron complexes, reaction with CO, 201 iron hydrazobenzene complex 258 iron hydride complexes 177 iron nitride 73 iron whisker catalysts for FT synthesis 66 iron zinc catalysts, for FT synthesis 44 iron/amine catalysts for methanol homol-

ogation 128 iron/cobalt cluster, supported on modified

silica 69 iron/zeolite catalysts 72 isobutyric esters, synthesis from CO, 191 isocyanate synthesis, from HCN 220 isocyanhydric acid 222 isomerization

alkanes 286 nitriles 227

isonitriles, synthesis by hydrocyanation 231 isoprene

hydrocyanation of 229 reaction with CO, 194 synthesis from methanol 96

isopropanol, homologation of 121 istope labeling 277 isotopic labeling experiments 284

Jolly, P. W. 175

Kellogg process 44 Kellogg/Synthol circulating fluidized bed

reactor 47 Kellogg/Synthol process 61, 68

product distribution 46 ketenes 23, 25,277 ketocaproic ester, synthesis from ethylene

140

306 INDEX

ketocarbenes, addition to nit riles 277 ketones, reaction with HCN 232 Keulcman's rule in olefin hydroformylation

122 kinetic control in FT synthesis 52 kinetics of CO hydrogenation 74 Knapsack process, synthesis of 220 Kochi, J. K. 280 Kolomnikov, I. S. 120 Kroper, H. 120

lactones 191-195 Lewis acid, see also reduction of CO 226

as cocatalysts 113 ligands

effect of, in methanol homologation 113

influence on alkane activation 253 light oil, from FT synthesis 49 linear i-olefins, one-stage syn thesis 72 liquid fuels, alternative sources 41 liquid hydrocarbons, from FT synthesis 41 lysine, synthesis from acrylonitrile 235

magn9titc 57 maieonitrile 219,234 manganese/iron catalysts 69 maximum weight fraction WIl 54 mechanism

for methanol carbonylation 131 for methanol homologation 120

with Co/I/P-catalysts 125 of carbonylation reactions 150 of olefin metathesis 283

melamine 241 synthesis of 238

metal carbcne complexes 268 metal carbonyls deposited in Y zeolites 70 metal dispersion 58 metal-carbon bonding 9,92

formation 151 metal-hydrogen bonds 151 metal-oxygen bonding 9,92 metallacyc!obutane, formation of 283 metallo enzymes, activation of alkanes 257 metallocarboxylate esters 171 metallocarboxylic acids 175 metathesis 20,95,206,263,283

mechanism for FT synthesis 66

reaction, catalysts for 284 mcthacrylonitriie 219

synthesis of 234 methanation of CO 2 184 methane 245

activation 251 by superacids 254

biological oxidation of 251 carboxylation of 249 chlorination of 252 condensation reactions 250 enzymatic oxidation of 251 formation 291 hydrocarbons 250

in FT synthesis 50 in methanol homologation 108, 126

from CO/H, 42 halogenation of 246 hydrogen-<ieuterium exchange 285 in nature 254 oxidation of 248 polymerization of 250 production of, by coal gasification 246 reaction

with carbenes 250 with CCl4 250 with SO, 249

selectivity, effect of reaction parameters on 68

synthesis from CO, 134 methane-ammonia reactions 220 methanol 31, 33

activation of 120 ammonoxidation of 220 as fuel 93 by oxidation of methane 248 C-O bond scission of 120 catalysts 90 cracking of 95 formation of 291 homologation 105

CO, as a by-product 128 cobalt catalyzed 107 continuous gas phase processes 117 effect of catalyst composition 109 heterogeneous catalysts for 117 historic developments 107 iron catalysts 128 poten tial use of 106

INDEX 307

methanol (continued) homologation (continued)

product composition 108, 109 reaction parameters 108 rhodium catalysts for 130, 131 ruthenium catalysts for 129 secondary reactions 108 side products 107, 127

oxidative addition of 123 processes 90 raw materials for 94 synthesis from CO, 183 use of 89,93

methionine, synthesis from acrolein 235 methoxy

clusters 9 complexes 9, 31, 92

methoxycarbonylation 138 methyl acetate 98, 100 methyl acrylate, synthesis from acetylene

138 methyl chloride, by chlorination of methane

252 methyl cobalt

complex 125 intermediate 120

methyl formate 33,90,97,102 methyl iodide

as promoter 112 nucleophilic attack on 124 oxidative addition of 124 to rhodium 130 reaction with CO(CO)4 124 role of in methanol homologation 123

methyl iron carbonyl intermediate 129 methyl methacrylate 98,101 methyl migration 125 methylamine, formation of 241 methylation

of CO 14 of pyridine 250

methylene 263 as a building block 82 bridge, formal insertion of CO into 77 bridged complexes 14, 24, 28, 76, 77,

122 alkylacetates from 122 as model compounds 66

carbenoids 287

complexes 286 dimerization of 287 groups

insertion of 67 polymerization of 75

polymerization of 287 reaction with olefins 288

methylene imine 220 methylenecyclopropanes 194 methylpentane, chlorination of 257 migration of hydrogen 270 migratory aptitude 277 Mimoun, H. 257 mineral oil, world production 41 Mobil Oil dual stage process 71 Mobil process 93,95 model reactions for carbide hydrogenation

76 Moessbauer spectroscopy 62,64 molecular weight distribution

control 69 in FT synthesis 42,52

molybdenum alkoxides 178 molybdenum amides 182 molybdenum complexes 285

reaction with CO, 200 molybdenum hydride complexes 177 monoaddition of HCN 225 monocarbonylation of acetylene 138 Monsanto process 130

production of propionic acid 141 Moss, R. A. 273 MTBE 89,93 multicenter bonding 18

n-iso ratio in hydroformylation 144, 145 Nagata reaction 232 Nakamura, A. 282 natural gas 245 neo-acids 155 nickel ally I

complexes 173 intermediates 227

nickel carbon dioxide complex 170 nickel catalysts 137

for methanol homologation 127 for FT syn thesis 42, 55

nickel catalyzed HCN addition 225 nickel complexes 225

308 INDEX

nickel complexes (continued) reaction with CO 2 201

nickel cyanides 228 nickel hydrides 226 nickel-phosphite complt:xes 226 nickela cyclopentadiene complexes 190 niobium carbon dioxide complex 170 nitrene 276 nitridation of iron catalysts 57 nitrided iron catalysts 73 nitriles

from cyanogen 248 synthesis of 248

nitriloacetonitrilc 235 noble metals as cocatalysts in homologa-

tion 116 norbornadiene, hydrocyanation of 230 norbornene 283 norcaradienc 275 nuclcophilic attack of alcohols 127

onto CO 161 nucleophilic carbenes 266

octatriene, hydrocyanation of 229 Olah, G. A. 254 olefin

insertion into Ni-H bonds 226 manufacture from CO 71 mctathesis 283 sell'ctivity, effect of reaction para-

oxamide 219 oxamide synthesis 238

from HCN 236 oxazole derivatives, synthesis of 278 oxazolidinones 198 oxidation

of HCN 241 of methane 248

oxidative addition of alkyl halides 153 ofC-X 153 of HCN 222 of Hydrogen 125 of iodine 125 of methanol 123 of methyl iodide 124

to a coba\t(l) species 125 carbonylation reactions 101

oxidoreduction processes 256 oxirene intermediates 277 oxometallocyclobutane complexes 196 oxycarbene

complexes 290 dimerization of 290

oxychlorination 247 oxycyanation

of l'lhylene 230 of ole fins 230

oxygenated C, products by methanol homologation 106

meters on 68 formation over rhodium catalysts 73 , 74 olefins oxygenated products 82

as primClry products in FT synthesis formation of 77 55 formation over niuided iron catalysts

from FT synthesis 42 73 hydrocyanation of 223 from FT synthesis 42 oxycyanation of 230 secondary reactions in FT synthesis 55 synthesis from methanol 94

oligomnization of CO 25 Olive, S. 289 organic carbonates. synthesis of 157 organozinc compounds 171 osmium catalysts for methanol homol­

ogation 127 oxala tes

formation of 157 uses of 157

oxalic acid. synthesis from CO, 203

p-methoxy-bcnzyl alcohol, homologation of 121

palladium alkoxides 159 palladium allyl complexes 174, 194 palladium carboxylalkoxy complexes 160 palladium carboxylates 282

complexcs 198 palladium ca talysts

for methanol homologation 127 in hydrocyanation 230 in Reppc reactions 138

palladium catalyzed cyc1opropcnation 282

INDEX 309

palladium-copper catalyst systems 158 p-substituted benzyl alcohols, homologation

of 120 paraffins, from FT synthesis 42 Parshall, G. W. 287 pentadiene, hydrocyanation of 229 peptides, formation of 240 perdeuterated methanol, homologation of

122 pesticides 238 Pettit, R. 66,67 , 287 phantom singlet 264 pharmaceuticals from HCN 219 phase transfer catalysis 233 phenyl isocyanate 204 phosphine modified cobalt/iodine catalysts

107 phosphine/cobalt ratio, effect of in methanol

homologation 114 phosphines

as ligands 114 effect of, in methanol homologation 113

phosphite ligands 226 activity in hydrocyanation 228 in methanol homologation liS

photosynthesis 169 phthalonitrile, synthesis from benzene 231 Pichler, H. 290 Pichler-Schulz mechanism 79,80 piperylene, hydrocyanation of 229 pivalic acid 156 platinum hydride complexes 177 platinum metal surfaces 285, 286 platinum peroxycarbonate complexes 180 platinum(II) surfaces 64 poisons, for FT catalysts 59 polycarbenes 288 polycarbonatcs 195, 199 polymer chemistry of methane 251 polymt;rization 207

of HCN 239 of methane 250

polymethylcne, by fT synthesis 42 Ponc,' mt;chanism 82 pore size of support, effcct on selectivity

70 pore volume 61 precipitated cobalt catalysts 60 precipitated iron catalysts 60

preparation of FT catalysts 59 primary alcohols, homologation of 120 probability

of chain growth, in FT synthesis 42 of chain krmination, in FT synthesis

42 of product formation in FT synthesis

51 product distribution in commercial FT

processes 46 product sekctivity

control in FT synthesis 42,68 effect of triphcnyl phosphine 113

product separation in FT synthesis 49 production plants for FT synthesis 48 progression coefficient 53 promoters

copper, for FT catalysts 55 for FT catalysts 56 for olefin formation 71 in methanol homologation 112 other than iodine, in methanol homol­

ogation 113 potassium, for FT catalysts 55 structural, for FT catalysts 55

promoting effect of iodin e 107 propanediol formates 188 propanol, synthesis from CO, 184 properties of HCN 221 propionic acid, synthesis from CO, 191 propionic ester, synthesis from ethylene

140 propionitrile, synthesis of 230 propylene oxide , reaction with CO, 196 propyleneimine , reaction with CO 2 199 protonation of transition metal complexes

152 proto tropic rearrangement of coordinated

()icfins 270 pseudoccmcntite ps-Fc 3 C 62 pulse tc,'hniques, in FT synthesis 64 purine 219, 240

derivatives 240 pyrimidines 240 pyrones 190

raw material for the chemical industry 41

310 INDEX

rt:action conditions, effect of, in methanol

homologation 116 for methanol homologation 120 mechanism

of FT synthesis 75 parameters, efft:ct on product select­

ivity in FT 68 tempcrature, effect of, in methanol

homologation 117 time, effect of in methanol homo-

logation 119 rearrangement reactions 263 rearrangemen ts of carbenes 277 reduction of CO

by high pressure 31 by hydrogen 12 by lewis acids 10 by LiAlH4 II by metal hydrides 12 by strong acids 11

rcduction of CO, 183, 199 reductiVt: dimerization of formaldehyde

290 reductive elimination 80

of acetaldehyde 125 of iodine 125 of nitriles 226

reductive oligomerization of CO 42 regiuselectivity

for carbene insertion reactions 271 in hydrocyanation reactions 226 of carbenes 266

Reppe-hydroformylation 136 Rcppe-type chemistry 135 reserves of CO, 169 Rheinpreussen demonstration plant 48 rhenium amides 182 rhenium hydride complexes 177 rhudium carbonyl complexes, in hydro­

formylation 142 rhodium carbuxylates 282 rhodium

catalysts for methanol homologation 127

in hydroformylation 147 silica supported 73

complexes, reaction with CO, 201 rhodium hydride complexes 177

rhodium hydroxy complexes 180 rhodium trit1uoroacetate 283 rhodium, homologation catalyst ring enlargement

of aromatics 271 reactions 275

ring opening processes 275 Ritter reaction 236 Roe\cn,Otto 141 ruthenium

catalysts for methanol homologation

129 for FT synthesis 42,55 iodine promoters for 129

complexes cationic 127 in homologation 116

105

127,

compounds as hydrogenation catalysts for aldehydes 126

homologation catalysts 105 hydrogenation activity of 129

ruthenium acetyl intermediate 130 ruthenium alkoxides 180 ruthenium carbonyl on Y zeolites 71 ruthenium hydride complexes 177 ruthenium methyl intermediate 130 ruthenium/cobalt catalysts for homologa-

tion 115

Sabaticr, P. 43 Sapienza mechanism 82 Sasol

Sasol, FT production plant 41 Sasol, production capacity 45 synthol process 44

Schulz-Flory distribution 30. 54, 68 Schwarzheide comparative tests 53

for FT catalysts 44 secondary alcohols, homologation of 120 secondary ions mass spectrometry (SlMS)

58,64 secondary reactions

in methanol homologation 108 on zeolite catalysts 71

selective synthesis of alcohols from CO 72

selectivity in hydroformylation 144

INDEX 31 ]

selectivity (continued) index of carbenes 273 limitation in FT synthesis 54

shape sekctive catalysis 69 shape sdective FT synthesis 70 Shawinigan process 220, 248 side product formation

acid ca taly zed 127 in methanol homologation 127

side products, in methanol homologation 107

silver catalysis 281 single cell protein 93 singlet state of carbenes 263 Singleton,E.180 sintered iron catalysts 60 Skattcboel reaction 276 slurry bed process in FT synthesis 47 slurry bed reactors 47 SN2-type process 124, 130 S N 2-type reaction in homologation 121 solvents, effect of in methanol homologa-

tion 117 spl'cific activity 61 specific surface area 61 spin states, relative stability of 267 stcreosekctivity of carbene cycloadditions

271 steroids, synthesis of 232 stibines as ligands 114 Storck 290 Strecker syn thesis 234 strong metal support interaction (SMSI) 58 styrene 283

from methanol 97 succinates, formation of 164 succinimide, synthesis of 232 succinonitrik 223

synthesis of 231 sulfur compounds, as catalyst poisons

59 superacids, activation of methane 254 supported catalysts for homologation 117 supports

for FT ca talysts 58 pore size of 69

surfac.: carbenc complex 80 species 66

surface carbide hydration of 66, 79 hydrogenation of 76, 77 species 68

surface carbon 63 hydrogenation of 65 on spent iron catalysts 63

surface CHx species 68 surface formyl

groups 65 SPecies 81

surface hydroxy car bene 65,78 surface hydroxyl group 81 surface methyl complex 80 surface methylene groups 67 surface species in FT synthesis 64 syn-anti distribution 266 syngas

composition, effect of, in methanol homologation 117

pressure, effect of, in methanol homo­logation 117

synthesis gas 245 production of HCN 221

synthetic natural gas 246 Synthol 43

t-butanol, homologation of 121,122 tantalum carbene complexes 269 telomerization reactions 206 temperature, effect of, in methanol homo-

loga tion 117 tertiary alcohols, homologation of 120 titanium alkoxides 178 titanium amides 180 titanium complexes, reactions with CO 2

173 transition metal carbenoids, nucleophilic

charackr of 289 trans-octenes 283 trialkylphosphines as ligands in methanol

homologation 115 triazine 219 trimethylamine 241 trimethylenemethane, insertion of CO, 195 triplet state of carbenes 263 Tropsch, H. 43 tungsten alkoxides 178 tungsten amidcs 182

312 INDEX

tungsten hydride complexes 177 Y zeolites, iron carbonyls on 70 tungsten, dinuclear carbene complexes of ylide intermediates 274

285

used FT catalysts, hydrolysis of 77

Vaska, L. 180 vinyl acetate 98, 100 vinyl aluminate, reaction with cyanogen

236 vinyl chloride, formation of 250 vinyl esters, reaction with hcn 231 vinyl copper compounds 171 vinylcycJohexene, hydrocyanation of 230

Wacker type catalysts 156 water gas shift reaction 50, 136 Webster, D, E. 252 Wender, I. 107 Wender mechanism 120 Wilkinson catalyst 191 Wolff rearrangement 277

X-ray diffraction analysis 62 X-ray photoemission spectroscopy (XPS)

57 , 64

zeolite catalysts 95,101 in FT synthesis 55 cobalt clusters 72 ruthenium catalysts 70 supercages 58 supported catalysts 72

zeolites as catalyst supports 58 chain limitation by 70 secondary reaction on 71

ZiegJer-Natta catalysts 27 Ziegler-type catalysts 253 Ziesecke mechanism 122 zinc alkoxides 178 zinc amides 180 zinc compounds, reactions with CO, 171 zirconium alkoxides 178 zirconium amides 180 zirconium complexes 200 zirconium hydride complexes 176 ZSM-5 72,95