Recent Progress in Chemistry of Endohedral Metallofullerenes

Tsuchiya, Takahiro; Akasaka, Takeshi; Nagase, Shigeru

doi:10.1002/9780470660188.ch10

Cited by 4 publications

(5 citation statements)

References 148 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Exohedral chemical functionalization of endohedral fullerenes has a great significance toward their potential applications. Although a large number of experimental studies on the chemical functionalization of empty fullerenes such as C 60 and C 70 have been already reported, methods developed for the exohedral functionalization of endohedral fullerenes are not so extended, and include photochemical reactions, Diels–Alder reactions, Prato reactions, Bingel-Hirsch reactions, radical addition reactions, and some other addition reactions. − ,,,,,, The chemical reactivity of fullerenes is mostly determined by their π-system, and in many reactions fullerenes behave as extended polyalkenes with rich addition chemistry. In the view of the multiple addition sites available at each carbon cage, the question of the regioselectivity of the chemical derivatization is one of the most challenging in fullerene chemistry.…”

Section: Chemical Properties Of Endohedral Fullerenesmentioning

confidence: 99%

“…Since the discovery of Sc 3 N@C 80 in 1999 as the first NCF which has the higher yield than that of all other EMFs, clusterfullerenes has been the fastest-growing family of endohedral fullerenes. While the family of clusterfullerenes consists of nitride clusterfullerenes (NCFs), carbide clusterfullerenes (CCFs), hydrocarbide clusterfullerenes (HCCFs), oxide clusterfullerenes (OCFs), sulfide clusterfullerenes (SCFs), and carbonitride clusterfullerenes (CNCFs), most studies of chemical functionalization of clusterfullerenes have been focused on NCFs mainly due to the advances of their high-yield synthesis. ,,,,, …”

Section: Chemical Properties Of Endohedral Fullerenesmentioning

confidence: 99%

“…While the family of clusterfullerenes consists of nitride clusterfullerenes (NCFs), carbide clusterfullerenes (CCFs), hydrocarbide clusterfullerenes (HCCFs), oxide clusterfullerenes (OCFs), sulfide clusterfullerenes (SCFs), and carbonitride clusterfullerenes (CNCFs), 32 most studies of chemical functionalization of clusterfullerenes have been focused on NCFs mainly due to the advances of their high-yield synthesis. 25,26,32,44,844,845 8.3.1. Diels−Alder Reactions.…”

Section: Clusterfullerenesmentioning

confidence: 99%

“…Plenty of more or less specialized reviews and book chapters devoted to EMFs were published in the past decade, and here we mention only a few of them. The general progress in the field (often with particular author’s accounts) was discussed in refs − . Nitride clusterfullerenes were a subject of a detailed review by Yang and Dunsch in 2007 and by Echegoyen et al in 2009, , oxide clusterfullerenes were reviewed by Stevenson in 2011, whereas new advances in the field of clusterfullerenes were discussed in the ref .…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Endohedral Fullerenes

2013

View full text Add to dashboard Cite

a Abbreviations of the methods used for the structures elucidation of EMFs: X-ray: single crystal X-ray diffraction of the nonderivatized EMF; X-ray (Drv) − the same, but for the derivative of EMF; X-ray (Powder) − synchrotron X-ray diffraction studies of powder samples with subsequent Rietveld/MEM analysis; NMR − 13 C NMR; Vib − vibrational spectroscopy (IR and/or Raman); QC − quantum-chemical calculations; UV−vis − UV−vis-(NIR) absorption spectroscopy; HRTEM/EELS − high resolution transmission electron microscopy coupled with electron energy loss spectroscopy; Echem − electrochemistry.

show abstract

Section: Chemical Properties Of Endohedral Fullerenesmentioning

confidence: 99%

Section: Chemical Properties Of Endohedral Fullerenesmentioning

confidence: 99%

Section: Clusterfullerenesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Endohedral Fullerenes

2013

View full text Add to dashboard Cite

show abstract

“…The second part of this review is devoted to carbene additions to endohedral metallofullerenes (EMFs), the most up-to-date topic. − Recent progress has revealed that chemical reactivities of EMFs differ from those of empty fullerenes. − The difference arises from intramolecular electron transfer from the internal metal atoms to the carbon cages, resulting in a drastic change of their electronic structures. , Consequently, the internal metal atoms play an important role in controlling the chemical reactivities of outer cage carbons. The unique molecular and electronic structures of EMFs also represent a fascinating issue in computational chemistry.…”

Section: Introductionmentioning

confidence: 99%

Carbene Additions to Fullerenes

2013

Self Cite

View full text Add to dashboard Cite

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

show abstract