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Loading...The Chemistry of the Fullerenes
Andreas Hirsch
Contents
Chapter 1 The Parent Fullerenes
The Fullerenes: Molecular Allotropes of Carbon . 2
Fullerene Production 7
Fullerene Generation by Vaporization of Graphite 7
Arc heating of Graphite 10
Solar Generators . 10
Inductive Heating of Graphite 11
Fullerene Synthesis in Combustion 11
Formation of Fullerenes by Pyrolysis of Naphthalene . 12
Endohedrals 12
The Formation Process . 15
Properties 25
Structures 25
The Discovery of the Fullerenes 5
Resitive Heating of Graphite 7
Separation and Purification 21
Physical and Spectroscopic Properties . 29
References 33
Chapter 2 Reduction . 37
2.1 Introduction 38
2.3 Reductive Electrosynthesis 42
2.3.1 Electrocrystallization 42
2.3.2 Electrophilic Additions to Fulleride Anions 43
2.4 Reduction with Metals . 44
2.4.1 Alkali Metal Fullerides . 44
2.4.1.1 Generation in Solution and Quenching Experiments . 44
2.4.1.2 Synthesis and Properties of Alkali Metal Fulleride Solids . 45
2.4.2 Alkaline Earth Metal Fullerides . 50
2.4.3 Reduction with Mercury . I . 51
2.5 Reduction with Organic Donor Molecules . 51
References 53
2.2 Fulleride Anions . . 38
Chapter 3 Nucleophilic Additions 56
3.1 Introduction 57
3.2 Addition of Carbon Nucleophiles 57
3.2.1
3.2.2
Hydroalkylation and Hydroarylation of C60 and C, 0 . 57
Langmuir – Blodgett Films of c60Ht-B~ . 63X Contents
3.2.3
3.2.4
3.3
3.4
References 77
Chapter4 Cycloadditions 79
Addition of Macromolecular Carbanions.Fullerene Polymers 64
Cyclopropanationof C60 and C70 66
Addition of Amines . 73
Addition of Hydroxide . 76
Introduction 80
[4+2] Cycloadditions 80
[3+2] Cycloadditions 87
Addition of Diazomethanes. Diazoacetatesand Diazoamides . 87
Addition of Trimethylenemethanes 99
Addition of Azomethine Ylides . 103
Addition of Azides . 99
Addition of Nitrile Oxides 105
Addition of Sulfinimides 106
Addition of Disiliranes . 106
Addition of Benzyne . 107
Addition of Enones . 107
Addition of Quadricyclane . 108
Addition of Electron Rich Alkynes . 109
[2+1] Cycloadditions 111
Addition of Carbenes 111
Addition of Silylenes 111
[2+2] Cycloadditions 107
Photopolymerization of C60 . 110
References 112
Chapter 5 Hydrogenation 115
5.1 Introduction 116
5.2 OligohydrofullerenesC60Hznand C70Hzn(n = 1- 6) . 116
5.2.1 Hydrogenation via Hydroboration, Hydrozirconation and Zinc/Acid Reduction 117
5.2.2 Theoretical Investigations 119
5.3 PolyhydrofullerenesC60Hznand C70Hzn(n = 7 – 70) . 125
5.3.1 Birch- Huckel Reduction 125
5.3.2
5.3.3 CatalyticHydrogenation . 129
5.3.4 Theoretical Investigations 129
References 134
Transfer Hydrogenation of c60and c70 . 127
Chapter 6 Radical Additions 136
6.1 Introduction 137
6.2 ESR Investigationsof Radical Additions . 137Contents XI
6.2.1 Addition of Single Radicals . 137
6.2.2 Multiple Radical Additions 143
6.3 Metalation of c60 with Pentacarbonylrhenium Radicals . 146
6.4 Hydrostannylation of C60 147
6.5 Addition of Bis(trifluoromethy1)nitroxide . 147
6.6
References 148
Radical Copolymerization of c60 and Paracyclophane 147
Chapter 7 Transition Metal Complex Formation 150
7.1 Introduction . 151
7.2 (q2-c6())Transition Metal Complexes 151
7.3 Hydrometalation Reactions . 159
7.4 Organopalladium Polymers of C60 . 160
References 160
Chapter 8 Oxidation and Reactions with Electrophiles . 162
8.1 Introduction 163
8.2
8.3 Oxygenation . 163
Electrochemical Oxidation of c60 and CTO
8.4 Osmylation . 166
8.5 Halogenation 172
8.5.1 Fluorination 172
8.5.2 Chlorination 175
8.5.3 Bromination
8.5.4 Reaction wit
8.6 Reactions with Strong Oxidizing Reagents and Acids 180
8.7 Reaction with Lewis Acids and Fullerenation of Aromatics . . 182
References 183
Chapter 9 Principles and Perspectives of Fullerene Chemistry 185
9.1 Introduction 186
9.2 Reactivity . . 186
9.3 Regioche 190
9.4 The Future of Fullerene Chemistry 195
9.4.1 Multiple Addition Products with a Defined Three-Dimensional Structure 195
9.4.2 Heterofullerenes . 196
9.4.3 Ring-Opening and ohedrals . 196
9.4.4 Chemistry with Higher Fullerenes . 197
9.5 Perspectives for Practical Applications 197
9.6 Concluding Re 199
References . . 200
Index .
Adams’ catalyst, 81
N-(I-adamantyl)bis(trifluoromethyl)sulfin imide,
alkoxy radicals, 140
7-alkylidene-2,3-diazabicycloheptene,99
alkylthio radicals, 140
allylic radicals, 143
allyltributyltin,100
1 -aminobenzotriazole,107
arc heating, 1, 10
arc vaporization, 15
bis(ethylenedithio)tetrathiafulvalene,32
benchtop reactor, 8
7H-benz[de]anthracene,128
benzenesulfenyl chloride, 109
benzo[l8]crown-6, 82
benzocyclobutenes, 82
IH-benzotriazol-l-o1,97
benzyl N-(tert-butoxycarbony1)-L-glutamate,86
N-(benzyloxycarbony1)-Lalanine, 86
benzyl radicals, 143
benzyne, 107
Bingel, C., 66
Birch-Hiickel reduction, 115, 125, 126, 129
1,6-bis(aminomethyl)hexane, 83
bis(2,6-diisopropylphenyl)silylene, 111
bis-o-quinodimethane,81
bromination, 162, 177, 178, 179, 180
bromoacetophenone,66
BuckyclutcherHPLC, 107, 117
carbenes, 111
catalytic hydrogenation, 115, 125, 129
chlorination, 162, 175, 176
chlorofullerenes,175
Columbus,200
corannulene,5.26, 144, 197
18-crown-6,107
cyanopolyynes, 5
cyclo[n]carbons, 19,20
cycloadditions, 116
[2+11cycloadditions, 111
[2+2] cycloadditions, 107
[3+21 cycloadditions,87.90.99
L4+2] cycloadditions,80, 87
cyclodextrin,23
danglingbonds, 17, 18
dansyl chloride, 104
decachlorocorannulene,16
desyl chloride, 66
dialkyl peroxides, 140
1,8-diazabicyclo[5.4.O]undec-7-ene, 66,73, 106
4,13-diaza-[181-crown-6, 83
dicyanopolyynes,16
dicyclohexylcarbodiimide,97
Diederich, F., 23, 54, 199
Diels-Alder adducts, 81, 92
Diels-Alder reactions, 80
N,N-diethylpropynylamine,109
9,1O-dihydroanthracene, 127
1,2-dihydro-1,2-(carboxymethano)fuIlerene-60,96
106 2,5-dihydro-2,2-dimethoxy-5,5-dimethyl-
1,3,4-oxadiazole,111
I ,Cdihydro-1,4-epoxy-3-phenylisoquinoline, 80
dihydroquinidine, 169, 170
dihydroquinine, 169, 170
diisobutylaluminium hydride, 100
1,3-dimercaptobenzene, 83
2,3-dimethylbuta- 1,3-diene,87
4-(dimethylamino)pyridine,100
5,6-dimethylene-1,4-dimethyl-2,3-diphenylnorborn-2-en-
7-one, 85
dimethyldihydrofullerene-60,44
dimethyldioxirane,164
1,2-dioxetane, 165
1,3-dioxolane, 164
1,3-diphenylisobenzofuran,80
disiliranes, 106
DNA, 198
electrocrystallization,37,42,43
endohedral complexes, 1, 12, 14.21.29, 185, 186, 197,
ethylene-propyleneterpolymer, 75
Euler ‘s theorem, 2, 25
Fagan, P. J., 151
Faraday, M., 199
Fermi level, 50
ferrocene, 14,32, 104
ferromagnets,53, 198
flagellanes,65
fluorination, 162, 172, 173, 174, 177
fluoroacylperoxides, 145
fluoroalkyl iodides, 145
4-(4-fluoro-3-nitrobenzoyl)benzocyclobutene,83
Fowler, P. W., 27
fulleranes, I16
fulleroid, 88, 192, 195, 197
fullerylation, 162, 180, 182
giant fullerenes,5,21, 197, 199
Gomberg radical, 141
gravity feed generators,8
Grignard reagents,57.58, 174
Gutmann solvent donicity number, 39
halofluorocarbons,145
halogenation, 162, 172
Hawkins, J. M., 166
heterofullerenes, 12, 185, 196
hexamethylene diisocyanate, 94
higher fullerenes,2, 16,21,23,28,29,31,38,40, 185,
HIV protease, 95, 198
HIV reverse transcriptase, 95
Huckel calculations,5, 153
Huffman, D. R., 7,20
hydroalkylation,56,57,62, 116, 118, 191
hydroarylation, 56.57.62
198
197Index 203
hydroboration, 115, 116, 117,118
hydrofullerenes, 12,57,116, 117,129, 130
hydrogenation, 115,116,118, 125, 127, 128, 129,130,
hydrometalation reactions, 150,151,159
hydrostannylation, 136,148
hydrozirconation, 115,I16
hyperfluorination, 173,197
inductive heating, 1, 11
isoamyl nitrite, 107
isobenzofuran, 80,81
3-isochromanone, 82
isolated pentagon rule, 17, 18, 19,25,26,27
isoxazoline, 105
Jahn-Teller distortion, 40,52
Jahn-Teller ground state, 40
Jones, D. E. H., 5
KekulC structure, 119
Kratschmer, W., 7,20
Kroto, H.W., 5,6,200
Langmuir-Blodgett films, 56,63,198
lanthanum fullerenes, 13
laser vaporization, 5,6,12,13
Lewis acids, 162,163,182,183
living polystyrene, 65
lubricants, 197,199
magic acid, 180
Manolopoulos, D. E., 27
MeiBner-Ochsenfeld Effect, 50
metallofullerenes, 14
(p-methox yphenyl)diaoethane, 90
methyl 2-chloroacetylacetate, 66
N-methylglycine, 103,104
7-methyl-3-methylideneocta-1,6-diene, 87
N-methylpyrrolidine. 103
molecular ferromagnetism, 38
Miillen, K., 81
Mulliken charges, 59
myrcene, 87
nanotubes, 21
nitrile oxides, 105
norbornene, 109
nucleophilic additions,75,116, 170, 186,189,191
I-organo- 1,2-dihydrofullerenes-60,58,60
oligohydrofullerenes, 115,116
organolithium reagents, 57,58,174
organopalladium polymers, 150,160
Osawa, E., 5
osmylation, 162,166, 170,171
oxygenation, 162, 163,189
ozonolysis, 197
pentacarbonylrhenium radicals, 136,146
1-phenyl-l,2-dihydrofullerene-70, 62
phenylene-bis(diazomethane),93
phenylthiyl radical adducts, 140
Pirkle-type phases, 23
poly(bispheno1A hexamethyleneurethane), 94
polyaromatic hydrocarbons, 11, 16
polyfluorofullerenes, 172,173
131,132
polyhydrofullerenes.5, 115, 116,125,126,127,128,
polymethoxyfullerenes, 176
polynaphthyls, 12
polystyrene gel, 23
pyracylene, 170
pyramidalization, 186,191,193
pyrazoline, 87,90
pyridinium chlorochromate, 100
pyridinium p-toluenesulfonate, 100
quadricyclane, 108
o-quinodimethanes, 82
[5]radialene, 89
radical additions, 136,137,143,145
regiochemistry, 185, 190,191,192, 193,195,198
resistive heating, 7,9,10
retro-Diels-Alder, 80
Rubin, Y., 85
Schlegel diagram, 3,4,5, 26,177, 178, 179,190
sebacoyl chloride,93
self-assembled monolayers, 75
Sharpless cinchona alkaloids, 170
Smalley, R. E., 5,6,10
solar generators, I , 10, 198,199
Soxhlet chromatography, 22,23
spectroelectrochemistry,40
Stone-Wales rearrangement, 17,20
strain energy, 186
sulfinimides, 106
superconductors, 38,45,47,49,50,51,53, 198,199
tetrahydrofullerene-60, 117, 123,124
tetrakis(dimethylamino)ethylene, 52,53,198
1,1,2,2-tetrakis(2,6-dimethylphenyl)disilirane,106
I , I ,2,2-tetramesityldisilirane,106
1,1,3,3-tetramesityl-l,3-disilolane, 106
transfer hydrogenation, 127
transition metal complex formation, 150,151
transition metal complexes, 150,151,159
tri-0-acetylglycal, 100
trimethylenemethanes, 99
2-trimethylsilyloxy-1,3-butadiene,86
3-triphenylmethyl-5-oxazolidinone,104
Vaska’s complex, 155,157
Wudl, F., 8,199
X-ray lithography, 198
yttrium fullerenes
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