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Radical Reactions of Fullerenes and their Derivatives : Developments in Fullerene Science - Boris Tumanskii

Radical Reactions of Fullerenes and their Derivatives

Developments in Fullerene Science

Hardcover

Published: 31st December 2001
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The discovery of fullerenes, species belonging to the electronodeficient polyalkenes with weakly conjugated double bonds, has opened novel opportunities for the radical chemistry. Pioneering study in this field was performed by P. J. Krusic, E. Wasserman, P. N. Keizer, J. R. Morton, and K. F. Preston (Science, 1991, 254, 1184). The fullerenyl radical adducts formed via addition of atoms or free radicals to fullerenes have no analogs in organic chemistry. In fact, radicals in which the unpaired electrons are delocalized over the surface of a sphere or ellipsoid have never been studied before. The unusual character of the fullerenyl radicals is also due to the fact that they occupy a sort of intermediate position between the planar and tetrahedral radicals. Thus, the elucidation of the characteristic features of fullerenyl radicals and their reactivity by EPR spectroscopy, and the comparison of the results with those of quantum-chemical studies are of fundamental importance. Isolation of the products from homolytic reactions of fullerenes in bulk amounts opens the door to large-scale preparation of new organic and organoelement derivatives of including biologically active ones. Radical reactions of fullerenes find wide application in the synthesis of fullere- containing polymers with valuable photophysical characteristics. Ferromagnetism of the complex of with tetra(dimethylamino)ethylene found lends impetus to a search of novel methods for preparation of biradicals one unpaired electron of those is located on the fullerene cage while the other retained by the addend.

`The authors [...] have themselves made significant contributions to the development of the field [...]. The extensive reference list and the tabular data make the book a valuable reference source to the rapidly growing fulleren chemistry community.' International Journal of Quantum Chemistry, 97:889 (2004)

Contributorsp. v
Acknowledgementsp. vii
Prefacep. ix
Basic Data on Fullerenes and Free Radicalsp. 1
Features of Fullerenesp. 1
Basic Data on Free radicalsp. 4
Methods for Generating Free Radicals in Solutionp. 4
Cleavage of R--X and R--R Bonds as a Result of Photolysis or Thermolysisp. 5
Monovalent Residue Abstraction by Another Radicalp. 6
Generation of Free radicals via Reactions Catalyzed by Electron Transferp. 8
Reactions Occurring via Free Radicalsp. 9
EPR Fundamentalsp. 11
EPR Theoryp. 12
Main Parameters of EPR Spectrump. 14
g-Factorp. 14
Line Width and Shapep. 14
Hyperfine Coupling Theoryp. 16
Biradicalsp. 21
Quantum-Chemical Calculationsp. 22
Radical Addition to C[subscript 60]p. 25
Addition of Carbon-Centered Radicalsp. 25
Addition of Fluoroalkyl Radicalsp. 32
Hindered Rotation in Alkylfullerenyl Radicalsp. 38
Dimerization of The Alkylfullerenyl Radicalsp. 41
Rate Constants for the Addition of Alkyl Radicals to C[subscript 60]p. 44
Multiple Addition of Benzyl Radicalsp. 45
Multiple Addition of Benzyl Radicalsp. 45
Multiple Addition of Alkyl Radicalsp. 50
Multiple Addition of Fluoroalkyl Radicalsp. 51
Addition of S- and O-centered radicalsp. 54
Addition of Silyl Radicalsp. 57
Addition of Boron-Centered Radicalsp. 60
Addition of Boryl Radicalsp. 60
Addition of B-carboranyl Radicalsp. 61
Addition of Phosphoryl Radicalsp. 64
Monoaddition of Phosphoryl Radicalsp. 64
Multiple Addition of Phosphoryl Radicalsp. 68
Addition of Metal--Centered Radicalsp. 71
Addition of Pt--centered Radicalsp. 72
Addition of Re- and Sn--centered Radicalsp. 73
Addition of Atomsp. 73
Addition of Hydrogenp. 73
Monoadditionp. 73
Multiple Addition of Hydrogensp. 76
Addition of Halogensp. 76
Fluorinationp. 76
Chlorinationp. 78
Brominationp. 79
Radical Addition to C[subscript 70]p. 83
Addition of Carbon-Centered Radicalsp. 85
Addition of S- and O--centered Radicalsp. 91
Addition of B-centered Radicalsp. 93
Addition of Phosphoryl Radicalsp. 93
Addition of Atomsp. 98
Addition of Hydrogenp. 98
Addition of Halogen Atomsp. 99
Radical Addition to C[subscript 76]p. 101
Radical Addition to Fullerene Derivativesp. 111
Radical Reactions with Metal Complexes of Fullerenesp. 111
Reactions of Radicals with Organic Derivatives of C[subscript 60]p. 117
Addition of Hydroxyl Radicalsp. 117
Addition of Phosphoryl Radicalsp. 118
Paramagnetic Fullerene Derivatives with an Unpaired Electron on the Added Moietyp. 133
Nytroxyl Fullerene Derivativesp. 133
Benzoquinone Fullerene Derivativesp. 137
Phenoxyl Fullerene Derivativesp. 141
Radical Addition of Macromolecules to C[subscript 60]p. 143
Radical Polymerization in the Presence of Free Radical Initiatorsp. 143
Nitroxyl-Mediated "Living" Radical Polymerizationp. 148
Atom-Transfer Radical Polymerizationp. 150
Ion Radical Reactions of Fullerenesp. 157
The EPR spectra of C[subscript 60] Anion Radicalsp. 158
The EPR Spectra of Fullerene Cation Radicalsp. 164
Azafullerenes in Radical Reactionsp. 173
Endohedral Metallofullerenes in Radical and Ion Radical Reactionsp. 179
Addition Reactionsp. 180
Oxidation and Reduction Reactionsp. 182
Conclusionp. 185
Indexp. 189
Table of Contents provided by Syndetics. All Rights Reserved.

ISBN: 9781402001765
ISBN-10: 1402001762
Series: Developments in Fullerene Science
Audience: Professional
Format: Hardcover
Language: English
Number Of Pages: 193
Published: 31st December 2001
Publisher: Springer-Verlag New York Inc.
Country of Publication: US
Dimensions (cm): 23.5 x 15.5  x 1.91
Weight (kg): 1.05