Carbene Additions to Fullerenes

Abstract

CONTENTS 1. Introduction 7209 2. Carbene Addition to Empty Fullerenes 7210 2.1. Dihalocarbenes 7210 2.1.1. Dihalocarbene Additions to C 60 7210 2.1.2. Dihalocarbene Additions to C 70 7212 2.1.3. Dihalocarbene Additions to Fullerene Fragments 7213 2.2. Decomposition of Diazo Compounds 7215 2.2.1. Thermolysis of Diazo Compounds 7215 2.2.2. Photolysis of Diazo Compounds 7223 2.2.3. In-Situ Generation of Diazo Compounds 7223 2.2.4. Isomerization of Fulleroids to Methanofullerenes 7228 2.3. Decomposition of Diazirines 7233 2.3.1. Chemical Probe 7233 2.3.2. Photoaffinity Labeling 7237 2.3.3. Fullerene Sugars 7237 2.3.4. Addition−Elimination Reaction 7238 2.4. Decomposition of Diazonium Salts 7238 2.5. Alkoxycarbenes 7238 2.6. Vinylcarbenes 7239 2.7. Basic Treatment of Malonates in the Presence of Iodine 7240 2.8. Photolysis of Benzocyclobutenediones 7240 2.9. α-Ketocarbenes 7240 2.10. Fischer Carbene Complexes 7241 2.11. Heterocyclic Carbenes 7242 2.12. Zwitterionic Intermediates 7244 2.13. Si and Ge Analogues of Carbenes 7244 2.13.1. Silylene Addition to C 60 7244 2.13.2. Silylene Addition to C 707245 2.13.3. Germylene Addition to C 60 7245 3. Carbene Additions to Endohedral Metallofullerenes 7245 3.1. Endohedral Metallofullerenes 7245 3.2. M@C 2v (9)-C 82 7246 3.2.1. Photolysis of Diazirines 7246 3.2.2. Thermolysis of Diazomethanes 7248 3.2.3. In-Situ Generation of Diazo Compounds 7248 3.2.4. Metal-Catalyzed Reactions 7248 3.2.5. Zwitterionic Intermediates 7248 3.3. M@C s (6)-C 82 7249 3.4. M 2 @I h (7)-C 80 7249 3.4.1. Photolysis of Diazirines 7249 3.4.2. In-Situ Generation of Diazo Compounds 7251 3.5. M 2 @D 3h (5)-C 78 7251 3.5.1. Photolysis of Diazirines 7251 3.5.2. Thermolysis of Diazirines 7252 3.6. M 2 @D 2 (10611)-C 72 7252 3.7. M 3 N@I h( 7)-C 80 7252 3.7.1. In-Situ Generation of Diazo Compounds 7252 3.7.2. Silylenes 7253 3.8. Sc 2 C 2 @C 3v (8)-C 82 7254 3.9. Sc 2 C 2 @C 2v (5)-C 80 7254 3.10. Sc 3 C 2 @I h (7)-C 80 7255 3.11. Li@C 60 7255 4. Concluding Remarks 7256 Author Information 7257 Corresponding Author 7257 Notes 7257 Biographies 7257 Acknowledgments 7258 References 7258

Modern Organic Synthesis with α-Diazocarbonyl Compounds

“…288−295 In general, these reactions are carried out thermally, and reactions with C 60 fullerene result in a mixture of three regioisomers, identified as the [6,6]-closed methanofullerene and the two [5,6]-open fulleroids. 296 Recently, Tuktarov and co-workers investigated cycloaddition of diazothioates to C 60 under thermal and catalytic conditions. 295 It was found that, in the presence of a palladium-based three-component catalyst, the selective formation of methanofullerenes was observed.…”

Hybrids of Fullerenes and 2D Nanomaterials

“…[106][107][108][109] Unlike pristine fullerene, with limited solubility in organic solvents, upon derivatization the grafted functional groups onto the fullerene's cage not only improves the solubility of fullerene but also provides additional reaction sites for further covalent hybridization with graphene. [106][107][108][109] Unlike pristine fullerene, with limited solubility in organic solvents, upon derivatization the grafted functional groups onto the fullerene's cage not only improves the solubility of fullerene but also provides additional reaction sites for further covalent hybridization with graphene.…”

Building Carbon Bridges on and between Fullerenes in Helium Nanodroplets

“…Carbene additions to fullerenes have already attracted considerable attention. 8 Carbenes should also play a similar role in interstellar chemistry. 37 Our experiments demonstrate the reactivity of C 60 (C:) n toward H 2 and H 2 O.…”