1.978-94-009-7040...deoxygenation of 199 dimerization of 203 disproportionation of 199 formation in...
Transcript of 1.978-94-009-7040...deoxygenation of 199 dimerization of 203 disproportionation of 199 formation in...
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