Strained Hydrocarbons: Beyond the vant Hoff and Le Bel Hypothesis

Presenting comprehensive and up–to–date state of the domain of highly strained hydrocarbons with unusual spatial structure, an experienced editor and top authors cover the whole range of these important molecules from [1.1.1]propellane to fullerenes and nanotubes. The necessity of studies in this area encompassing sometimes exotic molecules is discussed in detail showing their importance for basic science and practical applications. The fact that the latter cannot mostly be foreseen is amply documented.
Even not long ago, studying such molecules was an elitist activity, few synthetic chemists succeeded in their syntheses. Today, the field has broadened in view of emerging practical application and fullerenes and nanotubes are one of the most vividly developing domains.
Chapters include both experimental and theoretical studies. The former cover syntheses and unusual physicochemical properties related to the strain and untypical geometry of the molecules under scrutiny. The latter show importance of model calculations which help precise basic ideas of chemistry, such as the chemical bond, on the one hand, and are used to propose novel plausible synthetic targets, on the other.
The monograph aims not only at PhD students and newcomers in the field who seek for an introduction to this area but also at the specialists who want to obtain a broader perspective of this domain and make use of a comprehensive review of literature.

INTRODUCTION
Initial Remarks
Hydrocarbons with Unusual Spatial Structure: The Need to Finance Basic Research
Computations on Strained Hydrocarbons
Gallery of Molecules That Could Have Been Included in this Book
DISTORTED SATURATED HYDROCARBONS
Molecules with Inverted Carbon Atoms
Molecules with Planar and Pyramidal Carbon Atoms
A Theoretical Approach to Study and Design of Prismane Systems
(CH)2n Cage Structures, ′in′–′out′ Isomerism in Perhydrogenated Fullerenes and Planar Cyclohexane Rings
Ultralong C–C bonds
Ultrashort C–C bonds
DISTORTED ALKENES
Nonplanar Alkenes
Small Ring and Cage Structures Involving Nonplanar C=C Bonds
Strained Cyclic Allenes and Cumulenes
STRAINED AROMATIC MOLECULES
Nonstandard Benzenes
Distorted Cyclophanes
Helicenes
Cycloproparenes
FULLERENES
Introduction
Chemistry Influenced by the Nontypical Structure: Modification of [60]Fullerene
Physicochemical Properties and the Unusual Structure of Fullerenes
Fullerene Aggregates
Endohedral Fullerenes with Neutral Atoms and Molecules
Hydrogenated Fullerenes
Applications of Fullerenes
CARBON NANOTUBES
The Structure and Properties of Carbon Nanotubes
The Functionalization of Carbon Nanotubes
Applications of Carbon Nanotubes
ANGLE–STRAINED CYCLOALKYNES
Introduction
Cyclopropyne and Cyclobutyne: Speculations and Calculations on Non–Isolable Cycloalkynes
Cyclopentyne, Cyclohexyne, Cycloheptyne: From Reactive Intermediates to Isolable Compounds
The Isolable Angle–Strained Cycloalkynes: Cyclooctyne, Cyclononyne, and Beyond
Cyclic Polyacetylenes
Spectroscopic Properties of Angle–Strained Cycloalkynes
MOLECULES WITH LABILE BONDS: SELECTED ANNULENES AND BRIDGED HOMOTROPILIDENES
Introduction
Annulenes
Cyclooctatetraene
Bond Shifting, Ring Inversion and Antiaromaticity
Valence Isomerization
Ions Derived from COT
The Higher Annulenes
Bridged Homotrophilidenes
Recent Developments
MOLECULES WITH NONSTANDARD TOPOLOGICAL PROPERTIES: CENTROHEXAINDANE, KURATOWSKI′S CYCLOPHANE AND OTHER NONPLANAR MOLECULES
Introduction
Topologically Nonplanar Graphs and Molecular Motifs
Centrohexaindane
K5 Versus K3,3 Molecules
Kuratowski?s Cyclophane
SHORT–LIVED SPECIES STABILIZED IN ′MOLECULAR′ OR ′SUPRAMOLECULAR FLASKS′
CONCLUDING REMARKS


Helena Dodziuk worked for many years at the Institute of Organic Chemistry, at present at the Institute of Physical Chemistry, both of Polish Academy of Sciences. She is author or coauthor of over 100 publications, among them four books (one in Polish), 13 reviews and some popular articles. In addition to strained hydrocarbons with unusual spatial structure, she is interested in conformational analysis of hydrocarbons, classification of chiral molecules and isomers, NMR spectra and model calculations of cyclodextrin complexes, endohedral fullerene complexes and carbon nanotubes.

?It provides a nice overview of the subject and some in–depth discussions of selected topics in the field. Everyone from students to seasoned experts will find interesting new molecules to ponder in this book, including some that have yet to be synthesized.? ( Angewandte Chemistry, September 2009)

?This comprehensive review of current literature is intended for PhD students, readers interested in learning about the field, and specialists. The book is clearly illustrated and well–written.? ( Book News, September 2009)

?I would emphasize that any organic chemist who picks up this volume and leafs through it will have difficulty putting it down again. Almost every section stimulates fresh thoughts and research ideas.? (The Journal of the American Chemical Society, July 2009)