1. 1 Abstract: Cycloaddition of bromomalonates to Y 3 N@C 80 unexpectedly gave rise to fulleroid derivatives with unusually high stability. Complete characterization of these derivatives is described including X-ray crystallography, 1 H NMR, 13 C NMR, HMQC, UV-visible, HPLC, MALDI-MS, and electrochemistry. Density functional theory calculations are also presented, which provide a rationale for the formation of the fulleroid and reveal the underlying thermodynamic basis for their stability.

2. 2 “Open Rather than Closed” Malonate Methano-Fullerene Derivatives. The Formation of Methanofulleroid Adducts of Y 3 N@C 80 Olena Lukoyanova, Claudia M. Cardona, Jose´ Rivera, Leyda Z. Lugo-Morales, Christopher J. Chancellor, Marilyn M. Olmstead, Antonio Rodrı´guez-Fortea, Josep M. Poblet*, Alan L. Balch, and Luis Echegoyen* J. Am. Chem. Soc. 2007, 129, 10423-10430 演講者：莊雲婷

3. 3 Properties of C 60 Six-membered ring : 20 Five-membered ring : 12 [5,6] bonds : 60 (bond length : 1.45Å) [6,6] bonds : 30 (bond length : 1.38Å) Averge diameter : 7.1 Å http://nano.nchc.org.tw/dictionary/c60.html

4. 4 Electrochemical Detection of C 60 6- Echegoyen. L. et. al. J. Am. Chem. Soc. 1992, 114, 3978-3980.

5. 5 13 C NMR Spectrum of C 60 in C 6 D 6 Jingcheng H,et al ; J. Phys. Chem. B 2006, 110, 68-74

6. 6 Mass Spectrum of C 60 Mehlig.K,at al ; J. Chem. Phys., 2003,119,5591-5600

7. 7 Properties of C 80 Six-membered ring : 30 Five-membered ring : 12 [5,6] bonds : 60 [6,6] bonds :60 Averge diameter : 8.2 Å http://www.fullereneinternational.com/fic/fullerenes.html

8. 8 Endohedral Metallofullerene ( EMF ) Stevenson, S.; et al. Nature 1999, 401, 55-57 Sc 3 N@C 80 Shinohara, H.; et al. Bioconjugate Chem. 2001, 12, 510-514

9. 9 Synthesis of Y 3 N@(N-ethylpyrrolidino-C 80 ) Echegoyen, L.et.al; J. Am. Chem. Soc. 2005, 127, 10448-10453 [5.6]&[6,6] Y3NY3N Diels-Alder cycloadduct

10. 10 [5,6] and [6,6] Junction for Cycloaddition Echegoyen, L.; et al. Angew. Chem., Int. Ed. 2006, 45, 8176-8180 [5,6] [6,6] [5,6] [6,6]

11. 11 Interconversion of [6,6] to [5,6] Y 3 N@pyrrolidino-C 80 Echegoyen, L.; et al. Angew. Chem., Int. Ed. 2006, 45, 8176-8180 [6,6] [5,6]

12. 12 Bingel-Hirsch Reaction http://en.wikipedia.org/wiki/Image:Bingel_reaction_mechanism.gif

13. 13 Retro-Cyclopropanation Reaction Echegoyen, L,et al ; Eur. J. Org. Chem. 2004,2299-2316.

14. 14 Synthesis Bingel-Hirsch Adducts 1, Y 3 N@C 80 -C(CO 2 Et) 2. Yield 85% 2, Y 3 N@C 80 -C(CO 2 CH 2 Ph) 2. Yield 76% ( ODCB )

15. 15 Cyclic Voltammetry of Compound 1

16. 16 MALDI-MS Spectrum of Comound 1 1, Y 3 N@C 80 -C(CO 2 Et) 2, after chemical reduction with sodium metal in THF. Matrix-Assisted Laser Desorption Ionization.

17. 17 Y 3 N@C 80 -C(CO 2 CH 2 Ph) 2 Sc3N@C80 C1-C9 1.421 Å. C1-C9 : 2.30 Å open

18. 18 Orientations of Fullerene Cage in 2 five-membered ring containing C1 on the left side six-membered ring containing C9 on the right side. six-membered ring containing C1 on the left side five-membered ring containing C9 on the right side. C1 C9

19. 19 Three Orientations of the Y 3 N Units in 2 0.7 occupancy 0.21 occupancy 0.09 occupancy 90 K

20. 20 1 H NMR Spectra of 2 dd d H H

21. 21 Heteronuclear Multiple Quantum Coherence (HMQC) and Heteronuclear Multiple Bond Coherence (HMBC) are 2-dimensional inverse H,C correlation techniques that allow for the determination of carbon to hydrogen connectivity. HMQC is selective for direct C-H coupling and HMBC will give longer range couplings (2-4 bond coupling).

22. 22 13 C NMR Spectrum downfield

23. 23 HMQC Heteronuclear Multiple Quantum Coherence (HMQC) is selective for direct C-H coupling. http://www.chemistry.msu.edu/facilities/nmr/HMQC.html 13 C NMR 1 H NMR

24. 24 HMQC Spectrum 13 C NMR 1 H NMR

25. 25 UV-Visible Spectra

26. 26 Relative Position of the Y 3 N Unit in Y 3 N@C 80 -C(CO 2 CH 3 ) 2 isomer[5,6] [6,6] I1-73.0(4.8)-77.7(0.0) I2-60.4(17.4)-51.6(26.2) I3-74.4(3.4)-77.3(0.5) I4-73.8(3.9)-75.6(2.2) I5-45.7(32.1)-46.3(31.5) I6-57.0(20.7)-52.3(25.4) I7-48.5(29.3)-50.4(27.3) I8-49.5(28.2)-49.1(28.6) a BE =E[Y 3 N@C 80 -C(CO 2 CH 3 ) 2 ] - E[Y 3 N@C 80 ] -E[C(COOCH 3 ) 2 ]. b The calculations were using DFT with B3PW91 / 6-311G(2d,p) Bond Energiesa ab (in kcal mol-1) I1I3I4

27. 27 Bonding Energy for the most Stable 2 [6,6] Isomers I1I3I4 Angle α7.446.188.1 Relative energy0.00.52.2 I1 I3I4

28. 28 Distances of the [6,6]-Methano Derivative of Y 3 N@C 80 Distances(Å)X-rayDFT a Y1-N2.0662.081 Y2-N/Y3-N2.0702.072 C1···C92.292.277 C1-C81/C9-C811.5331.503 Y1-C1/Y1-C92.5282.549 a B3PW91 / 6-311G(2d,p)

29. 29 Representations of Functionalized La 2 @C 80 Y 3 N@C 80 La 2 @C 80 Distances(Å)I1I5M1M2 C81-C1 a 1.5031.5051.5001.490 C1···C9 a 2.2771.6572.2062.192 Charge transfer b 2.912.782.702.89 DFT Calaulation a B3PW91 / 6-311G(2d,p) b multipole derived charge method(MDC-q)

30. 30 Representations of Functionalized Sc 2 @C 80 La 2 @C 80 Sc 2 @C 80 Distances(Å)C 80 M1M2M3M4 C81-C1 a 1.5141.5001.490 1.512 C1···C9 a 1.6252.2062.1922.1841.646 Charge transfer b 2.702.891.020.53 DFT Calaulation a B3PW91 / 6-311G(2d,p) b multipole derived charge method(MDC-q)

31. 31 Rearrangement To Form the 2 Fulleroid Bingel-Hirsch Cycloaddition [6,6] [5,6] Norcaradiene Rearrangement OPEN

32. 32 Conclusions It is also apparent that the endohedral cluster plays a major role in directing the addition sites to EMFs. A possible thermally induced Norcaradiene rearrangement might occur instead subsequent to the [6,6]-addition to result in cleavage of the cyclopropane ring and formation of an opening in the fullerene cage. After a thorough experimental and theoretical characterization and analysis of the malonate monoadducts of Y 3 N@C 80, we conclude that their stability must be attributed to the cage-open fulleroid structure.

33. 33 Norcaradiene Rearrangement Joseph G, et al.; J. Am. Chem. Soc. 1999, 121, 6928-6935

34. 34 DFT

35. 35 Stevenson, S.; et al. Nature 1999, 401, 55-57