Foreword ........................................................ V
Preface ....................................................... VII
List of Contributors ......................................... XVII
1 Introduction ................................................. 1
1.1 Initial Remarks ......................................... 1
Helena Dodziuk
1.2 Hydrocarbons with Unusual Spatial Structure: the Need
to Finance Basic Research ............................... 5
Helena Dodziuk
1.3 Computations on Strained Hydrocarbons .................. 12
Andrey A. Fokin and Peter R. Schreiner
1.4 Gallery of Molecules That Could Have Been Included in
This Book .............................................. 18
Helena Dodziuk
1.4.1 Introductory Remarks ............................ 18
1.4.2 Saturated Hydrocarbons .......................... 18
1.4.3 Distorted Double Bonds .......................... 21
1.4.4 Benzene Rings with Nontypical Spatial
Structures ...................................... 22
1.4.5 Cumulenes ....................................... 25
1.4.6 Acetylenes ...................................... 26
References .................................................. 27
2 Distorted Saturated Hydrocarbons ............................ 33
2.1 Molecules with Inverted Carbon Atoms ................... 33
Kata Mlinarić-Majerski
2.1.1 Introduction .................................... 33
2.1.2 Small-ring Propellanes: Computational and
Physicochemical Studies ......................... 35
2.1.3 Small-ring Propellanes: Experimental Results .... 38
2.1.3.1 Preparation and Reactivity of
[1.1.1]Propellane ...................... 38
2.1.3.2 Preparation and Reactivity of
[2.1.1]Propellane and
[2.2.1]Propellane ...................... 41
2.1.3.3 [l.l.l]Propellane as the Precursor
for the Synthesis of Other Unusual
Molecules .............................. 42
2.1.4 New Hypothetical Molecules with Inverted
Carbon Atoms .................................... 43
2.2 Molecules with Planar and Pyramidal Carbon Atoms ....... 44
Helena Dodziuk
2.3 A Theoretical Approach to the Study and Design of
Prismane Systems ....................................... 49
Tatyana N. Gribanova, Vladimir I. Minkin and Ruslan
M. Minyaev
2.3.1 Introduction .................................... 49
2.3.2 Prismanes ....................................... 49
2.3.3 Expanded Prismanes .............................. 52
2.3.3.1 Asteranes .............................. 52
2.3.3.2 Ethynyl-expanded Prismanes ............. 54
2.3.4 Dehydroprismanes ................................ 55
2.3.5 Polyprismanes ................................... 56
2.3.5.1 Cubane Oligomers ....................... 56
2.3.5.2 Fused Prismanes ........................ 57
2.3.6 Conclusions ..................................... 58
2.4 (СН)2n Cage Structures, 'iri-'ouf Isomerism in
Perhydrogenated Fullerenes and Planar Cyclohexane
Rings .................................................. 59
Helena Dodziuk
2.4.1 (CH)2n Cage Structures .......................... 59
2.4.1.1 Tetrahedrane ........................... 61
2.4.1.2 Triprismane ............................ 62
2.4.1.3 Cubane 61, Cuneane 100 and
Octabisvalene 101 C8H8 ................. 62
2.4.1.4 C10H10 Saturated Cages .................. 63
2.4.1.5 C12H12 Saturated Cages .................. 63
2.4.1.6 Higher [n]Prismanes, Dodecahedrane ..... 64
2.4.1.7 'In'-'ouf Isomerism in
Perhydrogenated Fullerenes C60H60 ....... 64
2.4.1.8 Summary ................................ 67
2.4.2 Planar Cyclohexane Rings ........................ 67
2.5 Ultralong C-C Bonds .................................... 70
Takanori Suzuki, Takashi Takeda, Hidetoshi Kawai and
Kenshu Fujiwara
2.5.1 Introduction .................................... 70
2.5.2 Ultralong C-C Bonds Confined in a Stiff
Molecular Frame ................................. 72
2.5.3 Tetraphenylnaphthocyclobutene as a Scaffold to
Produce Ultralong C-C Bonds ..................... 73
2.5.4 'Clumped' Hexaphenylethane Derivatives with
Elongated and Ultralong C-C Bonds ............... 74
2.5.5 HPE Derivatives with a Super-ultralong C-C
Bond ............................................ 78
2.5.6 'Expandability' of the Ultralong C-C Bond:
Conformational Isomorphs with Different Bond
Lengths ......................................... 79
2.5.7 Future Outlook .................................. 82
2.6 Ultrashort C-C Bonds ................................... 82
Vladimir Y. Lee and Akira Sekiguchi
2.6.1 Introduction .................................... 82
2.6.2 Tricyclo[2.1.0.02,5]pentanes: Ultrashort
Endocyclic Bridging C-C Bonds ................... 83
2.6.3 Coupled Cage Compounds: Ultrashort Exocyclic
Intercage C-C Bonds ............................. 86
2.6.4 Sterically Congested m-Methylcyclophanes:
Ultrashort C-C(Me) Bonds ........................ 91
2.6.5 Conclusions ..................................... 91
References .................................................. 92
3 Distorted Alkenes .......................................... 103
3.1 Nonplanar Alkenes ..................................... 103
Dieter Lenoir, Paul J. Smith and Joel F. Liebman
3.1.1 Introduction and Context ....................... 103
3.1.2 Bridgehead Alkenes ............................. 103
3.1.2.1 t-Butyl-substituted Ethylenes ......... 104
3.1.2.2 Investigations of t-Butylated
Ethylenes and Other Acyclic Alkenes ... 106
3.1.2.3 Cyclo and Bicycloalkenes ... and on
to Polycyclic Analogs ................. 107
3.1.2.4 Adamantylideneadamantane and its
Derivatives ........................... 108
3.1.2.5 t-Butyl-substituted and Cyclic
Stilbenes ............................. 108
3.1.3 Multiply Unsaturated Bicycloalkenes,
Homoaromaticity and Cyclophanes ................ 109
3.1.3.1 The Most Distorted Ethylenes and
Seemingly Simple Analogs .............. 111
3.2 Small Ring and Cage Structures Involving Nonplanar
C=C Bonds ............................................. 112
Athanassios Nicolaides
3.2.1 Pyramidalized Alkenes .......................... 112
3.2.1.1 Tricyclo[3.3.11.03,7]
undec-3(7)-ene38 ...................... 115
3.2.1.2 Tricyclo[3.3.10.03,7]dec-3(7)-ene 39
and tricyclo[3.3.9.03,7]non-3(7)-ene
40 .................................... 117
3.2.1.3 Tricyclo[3.3.0.03,7]oct-l(5)-ene41 ..... 119
3.2.1.4 (Ph3P)2Pt Complexes ................... 119
3.2.2 Conclusions .................................... 121
3.3 Strained Cyclic Allenes and Cumulenes ................. 122
Richard P. Johnson and Kaleen M. Konrad
3.3.1 Introduction ................................... 122
3.3.2 Allene π Bond Deformations and Strain
Estimates ...................................... 123
3.3.3 Four- and Five-membered Ring Allenes ........... 124
3.3.4 1,2-Cyclohexadienes ............................ 125
3.3.5 1,2,4-Cyclohexatrienes ......................... 127
3.3.5.1 6-Methylene-l,2,4-Cyclohexatrienes
and Related Structures ................ 131
3.3.6 Seven-membered Ring Allenes .................... 131
3.3.6.1 Cycloheptatetraenes ................... 132
3.3.7 Eight-membered Ring Allenes .................... 134
3.3.8 Polycyclic Allenes ............................. 135
3.3.9 Cyclic Bisallenes .............................. 136
3.3.10 Cyclic Butatrienes ............................. 136
3.3.10.1 Butatriene π Bond Deformations and
Strain Estimates ...................... 137
3.3.10.2 Five- to Nine-membered Ring Cyclic
Butatrienes ........................... 137
3.3.11 Conclusions .................................... 139
References ............................................ 140
4 Strained Aromatic Molecules ................................ 147
4.1 Nonstandard Benzenes .................................. 147
Paul J. Smith and Joel F. Liebman
4.1.1 Introduction and Context ....................... 147
4.1.2 Alkylated Aromatics ............................ 148
4.1.3 Helicenes ...................................... 148
4.1.4 [njCirculenes .................................. 149
4.1.5 Cyclophanes .................................... 150
4.2 Distorted Cyclophanes ................................. 153
Henning Hopf
4.2.1 Introduction ................................... 153
4.2.2 The [n]Cyclophanes ............................. 154
4.2.2.1 [n]Paracyclophanes .................... 154
4.2.2.2 [n]Metacyclophanes .................... 160
4.2.3 The [m.rc]Paracyclophanes ...................... 161
4.2.4 Distorted Aromatic Rings and 'Aromatic
Character' ..................................... 164
4.2.5 NMR Characteristics of Cyclophanes ............. 165
4.3 Helicenes ............................................. 166
Ivo Starý and Irena C. Stará
4.3.1 Introduction ................................... 166
4.3.2 Synthesis of Helicenes ......................... 166
4.3.3 Nonracemic Helicenes ........................... 171
4.3.4 Intriguing Helicene Structures ................. 172
4.3.5 Physicochemical Properties and Applications .... 173
4.3.6 Theoretical Studies ............................ 175
4.3.7 Outlook ........................................ 176
4.4 Cycloproparenes ....................................... 176
Brian Halton
4.4.1 Introduction ................................... 176
4.4.2 Synthetic Considerations ....................... 177
4.4.3 Chemical Considerations ........................ 183
4.4.4 Heteroatom Derivatives ......................... 187
4.4.5 Physicochemical and Theoretical
Considerations ................................. 188
References ................................................. 193
5 Fullerenes ................................................. 205
5.1 Introduction .......................................... 205
Helena Dodziuk
5.2 Chemistry Influenced by the Nontypical Structure:
Modification of [60] Fullerene ........................ 208
Takuma Hara, Takashi Konno, Yosuke Nakamura and Jun
Nishimura
5.2.1 Introduction ................................... 208
5.2.2 General Overview ............................... 209
5.2.3 Modification Reactions ......................... 215
5.2.3.1 Reduction and Oxidation ............... 215
5.2.3.2 Alkylation ............................ 217
5.2.3.3 Cycloadditions ........................ 218
5.2.4 Conclusions .................................... 224
5.3 Physicochemical Properties and the Unusual Structure
of Fullerenes ......................................... 225
5.3.1 Single-crystal X-ray Structures of Fullerenes
and Their Derivatives .......................... 225
Olga V. Boltalina, Alexey A. Popov and Steven
H. Strauss
5.3.1.1 Introduction .......................... 225
5.3.1.2 Disorder .............................. 226
5.3.1.3 Nonplanar Steric Strain ............... 226
5.3.1.4 Nonplanar Steric Strain Parameters .... 229
5.3.1.5 Are Non-IPR Fullerenes Sterically
Unstable? ............................. 232
5.3.1.6 Long and Short C(sp2)-C(sp2) Bonds
in Fullerene Cages .................... 232
5.3.1.7 Steric Strain in C60(X)n Isomers ...... 236
5.3.2 Vibrational and Electronic Spectra ............. 238
Alexey A. Popov
5.3.2.1 Introduction .......................... 238
5.3.2.2 Vibrational Spectra of Fullerenes ..... 239
5.3.2.3 The Orbital Picture of Fullerenes:
High-energy Electronic Spectra ........ 243
5.3.2.4 Electronic Excitations. UPS,
UV/Vis/NIR Absorption and
Fluorescence Spectroscopy ............. 246
5.3.3 Nuclear Magnetic Resonance ..................... 250
Toni Shiroka
5.3.3.1 Introduction .......................... 250
5.3.3.2 NMR of Fullerenes ..................... 251
5.3.3.3 Concluding Remarks .................... 259
5.3.4 Electrochemistry ............................... 259
Renata Bilewicz and Kazimierz Chmurski
5.3.4.1 Electronic Properties of Fullerenes ... 259
5.3.4.2 Electrochemical Properties of
Soluble Fullerene Derivatives ......... 263
5.3.4.3 Electrocatalytic Activity of
Fullerenes ............................ 270
5.3.4.4 Conclusions and Outlook ............... 272
5.4 Fullerene Aggregates .................................. 273
Tommi Vuorinen
5.4.1 Film Preparation Methods ....................... 274
5.4.2 Fullerene Film Properties ...................... 277
5.4.3 Conclusions .................................... 282
5.5 Endohedral Fullerenes with Neutral Atoms and
Molecules ............................................. 282
Sho-ichi Iwamatsu
5.5.1 Introduction ................................... 282
5.5.2 Preparation .................................... 282
5.5.2.1 Direct Approach Using an Existing
Fullerene ............................. 282
5.5.2.2 Molecular Surgery Approach via an
Open-cage Fullerene ................... 284
5.5.2.3 Open-cage Fullerenes, Reversible
Molecular Incorporations and
Ejections ............................. 285
5.5.3 Properties ..................................... 287
5.5.3.1 Host Fullerenes ....................... 287
5.5.3.2 Guest Substrates ...................... 288
5.5.4 Binding Energies, Theoretical Investigations ... 290
5.5.5 Summary ........................................ 291
5.6 Hydrogenated Fullerenes ............................... 291
Mark S. Meier
5.6.1 Synthesis and Structure ........................ 291
5.6.2 C70Chemistry ................................... 295
5.6.3 Higher Fullerenes .............................. 297
5.6.4 Reactivity of Hydrogenated Fullerenes .......... 297
5.7 Applications of Fullerenes ............................ 299
Rossimiriam Pereira de Freitas and Jean-Frangois
Nierengarten
5.7.1 Introduction ................................... 299
5.7.2 Applications in Materials Science .............. 299
5.7.2.1 C60 Derivatives for Optical Limiting
Applications .......................... 299
5.7.2.2 C60 Derivatives for Photovoltaic
Applications .......................... 304
5.7.3 Biological Applications ........................ 310
5.7.4 Conclusions .................................... 314
References ................................................. 315
6 Carbon Nanotubes ........................................... 335
6.1 The Structure and Properties of Carbon Nanotubes ...... 335
Anke Krueger
6.1.1 I ntroduction .................................. 335
6.1.2 The Structure of Single-walled Carbon
Nanotubes ...................................... 335
6.1.3 The Structure of Multi-walled Carbon
Nanotubes ...................................... 342
6.1.4 The Aromaticity of Carbon Nanotubes ............ 345
6.1.5 Conclusions .................................... 347
6.2 The Functionalization of Carbon Nanotubes ............. 347
Anke Krueger
6.2.1 Introduction ................................... 347
6.2.2 Functionalization of the Nanotube Tips ......... 348
6.2.3 Non-covalent Functionalization of Carbon
Nanotubes ...................................... 349
6.2.4 Covalent Side-wall Functionalization of
Carbon Nanotubes ............................... 352
6.2.5 Endohedral Functionalization of Carbon
Nanotubes ...................................... 355
6.2.6 Conclusions .................................... 356
6.3 Applications of Carbon Nanotubes ...................... 356
Marc Monthioux
6.3.1 Introduction ................................... 356
6.3.2 Properties of CNTs ............................. 357
6.3.2.1 Which CNT for Which Application? ...... 357
6.3.2.2 Why is 'Nano' Beautiful? .............. 358
6.3.2.3 Potential Problems Related to the
Use of С NTs .......................... 360
6.3.3 Applications of CNTs ........................... 362
6.3.3.1 Prospective Applications .............. 362
6.3.3.2 Applications Under Development ........ 364
6.3.3.3 Applications on the Market ............ 366
6.3.4 Conclusions .................................... 367
References ............................................ 368
7 Angle-strained Cycloalkynes ................................ 375
Henning Hopf and Jörg Grunenberg
7.1 Introduction .......................................... 375
7.2 Cyclopropyne and Cyclobutyne: Speculations and
Calculations on Non-isolable Cycloalkynes ............. 376
7.2.1 Cyclopropyne and Related Systems ............... 376
7.2.2 Cyclobutyne .................................... 378
7.3 Cyclopentyne, Cyclohexyne, Cycloheptyne: from
Reactive Intermediates to Isolable Compounds .......... 379
7.3.1 Cyclopentyne and its Derivatives ............... 379
7.3.2 Cyclohexyne and its Derivatives ................ 382
7.3.3 Cycloheptyne and its Derivatives ............... 384
7.4 The Isolable Angle-strained Cycloalkynes:
Cyclooctyne, Cyclononyne, and Beyond .................. 385
7.4.1 Cyclooctyne and its Derivatives ................ 385
7.4.2 Cyclononyne and Cyclodecyne .................... 386
7.5 Cyclic Polyacetylenes ................................. 387
7.6 Spectroscopic Properties of Angle-strained
Cycloalkynes .......................................... 392
References ................................................. 393
8 Molecules with Labile Bonds: Selected Annulenes and
Bridged Homotropilidenes ................................... 399
Richard V. Williams
8.1 Introduction .......................................... 399
8.2 Annulenes ............................................. 399
8.2.1 Cyclobutadiene ................................. 399
8.3 Cyclooctatetraene ..................................... 403
8.4 Bond Shifting, Ring Inversion and Antiaromaticity ..... 405
8.5 Valence Isomerization ................................. 409
8.6 Ions Derived from COT ................................. 410
8.7 The Higher Annulenes .................................. 411
8.8 Bridged Homotropilidenes .............................. 413
8.9 Recent Developments ................................... 415
8.9 Conclusions ........................................... 419
References ................................................. 420
9 Molecules with Nonstandard Topological Properties:
Centrohexaindane, Kuratowski's Cyclophane and Other
Graph-theoretically Nonplanar Molecules .................... 425
Dietmar Kuck
9.1 Introduction .......................................... 425
9.1.1 Is All This Trivial? ........................... 425
9.2 Topologically Nonplanar Graphs and Molecular Motifs ... 427
9.2.1 The Centrohexaquinacene Core ................... 427
9.2.2 The Nonplanar Graphs K5 and K3,3 and Some
Molecular Representatives ...................... 428
9.3 Centrohexaindane ...................................... 430
9.3.1 Centrohexaindane and Structural Regularities
of the Centropolyindane Family ................. 431
9.3.2 Syntheses of Centrohexaindane .................. 433
9.3.3 Multiply-functionalized Centrohexaindanes ...... 436
9.4 Ks versus K3,3 Molecules .............................. 438
9.4.1 Topologically Nonplanar Polyethers and Other
K3,3 Compounds ................................. 438
9.5 Kuratowski's Cyclophane ............................... 441
9.5.1 Synthesis of Kuratowski's Cyclophane ........... 441
9.5.2 The Structure of Kuratowski's Cyclophane ....... 443
9.6 Conclusions ........................................... 444
References ................................................. 445
10 Short-lived Species Stabilized in 'Molecular' or
'Supramolecular Flasks' .................................... 449
Helena Dodziuk
References ................................................. 456
11 Concluding Remarks ......................................... 459
Helena Dodziuk
References ................................................. 461
Index ......................................................... 463
|
