Lewars Modeling Marvels

Computational Anticipation of Novel Molecules
1. Auflage 2008
ISBN: 978-1-4020-6973-4
Verlag: Springer Netherlands
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 282 Seiten

The aim of this highly original book is to survey a number of chemical compounds that some chemists, theoretical and experimental, find fascinating. This is the first book to feature compounds/classes of compounds of theoretical interest that have been studied theoretically but have defied synthesis. It is hoped that this collection of idiosyncratic molecules will appeal to chemists who find the study of chemical oddities interesting and, on occasion, even rewarding.

Autoren/Hrsg.

Lewars, Errol G.

Inhaltsverzeichnis

1;Preface;7
2;Contents;8
3;1 Planar Carbon;12
3.1; Introduction;12
3.2; Dimethanospiro[2.2]octaplane: A Computational Saga;14
3.3; Synthesis;20
3.4; Conclusions;21
3.5; Notes;22
4;2 Pyramidal Carbon;24
4.1; Introduction;24
4.2; Pyramidane;25
4.3; Other Molecules with Possibly Pyramidal Carbon;35
4.4; Synthesis;36
4.5; Conclusions;38
4.6; Notes;38
5;3 Oxirene;41
5.1; Introduction;41
5.2; The Oxirene Problem: History;43
5.2.1; Oxirenes to 1981; Summary;43
5.2.2; Oxirenes After 1981;49
5.3; Synthesis;59
5.4; Conclusions;60
5.5; Notes;60
6;4 Nitrogen Pentafluoride and Related Compounds;63
6.1; Introduction;63
6.2; Nitrogen Pentafluoride, the Octet Rule, and Hypervalency;63
6.3; The Predicted Properties of NF5;69
6.4; Related Nitrogen Compounds;71
6.5; Hypercoordinate Compounds of Other Nonmetals;72
6.6; Synthesis;72
6.7; Conclusions;73
6.8; Notes;74
7;5 Helium Compounds;76
7.1; Introduction;76
7.2; Overview of the Chemistry of Neon, Argon, Krypton, Xenon, (Radon);76
7.3; Helium Compounds;80
7.4; Synthesis;86
7.5; Notes;87
8;6 Tetrahedrane;90
8.1; Introduction;90
8.2; Counterfeit Chemistry: A Fictional Synthesis of a Tetrahedrane;91
8.3; Real Syntheses of Tetrahedranes;92
8.3.1; Tetra-t-butyltetrahedrane, Synthesis;92
8.3.2; Tetra-t-butyltetrahedrane, Properties;94
8.3.3; Tetrakis(trimethylsilyl)tetrahedrane, Synthesis;96
8.3.4; Tetrakis(trimethylsilyl)tetrahedrane, Properties;96
8.3.5; Tetrahedranyllithium (and Compounds Derived Therefrom);99
8.4; Tetra t-butyltetrahedrane, B3LYP/6-31G* Calculations;103
8.5; Tetrakis(trimethylsilyl)tetrahedrane, B3LYP/6-31G* Calculations;103
8.6; The Parent Tetrahedrane, Calculations;103
8.7; Some Calculated Properties of Tetrahedrane;105
8.8; Synthesis;109
8.9; Notes;110
9;7 Orthogonene;114
9.1; Introduction;114
9.2; Orthogonenes 1 and 4;116
9.3; Synthesis;119
9.4; Conclusions;121
9.5; Notes;121
10;8 Hexaphenylethane;123
10.1; Introduction;123
10.2; Hexaphenylethane: The Classical Period;123
10.3; Hexaphenylethane: The Modern Period;126
10.4; Synthesis;131
10.5; A Related Compound;134
10.6; Conclusions;136
10.7; Notes;136
11;9 Ethenedione, C2O2;138
11.1; Introduction;138
11.2; Electronic Structure and Stability of Ethenedione;138
11.3; Attempts to make Ethenedione;140
11.4; Species Related to Ethenedione;142
11.5; Synthesis;144
11.6; Conclusions;145
11.7; Notes;145
12;10 Nitrogen Oligomers and Polymers: Superfuels or Chimeras?;148
12.1; Introduction;148
12.2; Experimental Results;149
12.3; Theoretical Results;155
12.3.1; Cyclic N8 Molecules;155
12.3.2; Cyclic N6 Molecules;155
12.3.3; Cyclic N4 Molecules;162
12.3.4; Cyclic Polynitrogens with Several Rings;163
12.3.5; Acyclic Molecules;163
12.3.6; Some "Conventional" Polynitrogens;164
12.4; Synthesis;166
12.5; Conclusions;166
12.6; Notes;167
13;11 Oligomers and Polymers of Carbon Dioxide and CO2/N2;171
13.1; Introduction;171
13.2; CO2 Compounds;171
13.3; CO2--N2 Compounds;177
13.4; Structures (B3LYP/6-31G--) of the CO2--N2 Compounds (Fig. 11.5);181
13.5; Decomposition Reactions (B3LYP/6-31G-- and MP2/6-31G--) of the Cyclic CO2--N2 Compounds (Fig. 11.6);181
13.6; The B3LYP/6-31G* Reaction Profiles (Fig. 11.6);181
13.7; The MP2/6-31G* Reaction Profiles (Fig. 11.7);184
13.8; Stability of the Acyclic CO2--N2 Compounds 13a, 13b, 13c;184
13.9; Synthesis;186
13.9.1; The CO2 Compounds;186
13.9.2; The CO2 N2 Compounds;186
13.10; Summary;188
13.10.1; The CO2 Dimer etc., Stability;188
13.10.2; The CO2--N2 Dimer etc., Stability;189
13.10.3; Synthesis;189
13.11; Notes;189
14;12 Polyprismanes. Flights of Fun and Fancy;191
14.1; Introduction;191
14.2; Simple Prismanes;193
14.3; Polyprismanes;198
14.4; Some Computed Properties of Polyprismanes;207
14.5; Strain;208
14.6; Thermodynamic Stability;210
14.7; Kinetic Stability;215
14.8; Two Simple Reactions: Attack by a Hydride Ion and by a Proton;219
14.9; Other Candidates for Half-Planar or Linear C--C--C Carbons;224
14.10; Some Other Rodlike Molecules: Carbon Nanotubes, Staffanes, Ladderanes;226
14.11; Polyprismanes: Synthesis;228
14.12; Conclusions;230
14.13; Notes;230
15;13 A Menagerie of Molecules from Michl and Balaji: Superstrained Molecules;233
15.1; Introduction;233
15.2; Molecules 1, 2, and 3 (Known Species);233
15.3; Molecules 4, 5, 6, 7 (Unknown Species);241
15.4; A Comparative Survey of some Salient Characteristics of 1--7: Geometry, Strain, Ionization Energies, and IR and Electronic Spectra ;249
15.5; Synthesis;255
15.6; Conclusions;259
15.7; Notes;259
16;14 Summary;263
16.1; Introduction;263
16.2; Our Medley of Molecules, Arranged by Common Themes;264
16.3; Metamedley;276
16.4; Notes;278
17;Index;280