1 Abstract: Cycloaddition of bromomalonates to Y 3 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 “Open Rather than Closed” Malonate Methano-Fullerene Derivatives. The Formation of Methanofulleroid Adducts of Y 3 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, 演講者：莊雲婷

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

4 Electrochemical Detection of C Echegoyen. L. et. al. J. Am. Chem. Soc. 1992, 114,

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

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

8 Endohedral Metallofullerene ( EMF ) Stevenson, S.; et al. Nature 1999, 401, Sc 3 80 Shinohara, H.; et al. Bioconjugate Chem. 2001, 12,

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

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

11 Interconversion of [6,6] to [5,6] Y 3 80 Echegoyen, L.; et al. Angew. Chem., Int. Ed. 2006, 45, [6,6] [5,6]

12 Bingel-Hirsch Reaction

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

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

15 Cyclic Voltammetry of Compound 1

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

17 Y C(CO 2 CH 2 Ph) 2 C1-C Å. C1-C9 : 2.30 Å open

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 Three Orientations of the Y 3 N Units in occupancy 0.21 occupancy 0.09 occupancy 90 K

20 1 H NMR Spectra of 2 dd d H H

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 13 C NMR Spectrum downfield

23 HMQC Heteronuclear Multiple Quantum Coherence (HMQC) is selective for direct C-H coupling C NMR 1 H NMR

24 HMQC Spectrum 13 C NMR 1 H NMR

25 UV-Visible Spectra

26 Relative Position of the Y 3 N Unit in Y 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 C(CO 2 CH 3 ) 2 ] - E[Y 3 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 Bonding Energy for the most Stable 2 [6,6] Isomers I1I3I4 Angle α Relative energy I1 I3I4

28 Distances of the [6,6]-Methano Derivative of Y 3 80 Distances(Å)X-rayDFT a Y1-N Y2-N/Y3-N C1···C C1-C81/C9-C Y1-C1/Y1-C a B3PW91 / 6-311G(2d,p)

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

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

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

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 80, we conclude that their stability must be attributed to the cage-open fulleroid structure.

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

34 DFT

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