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1、1,Abstract:,Cycloaddition of bromomalonates to Y3NC80 unexpectedly gave rise to fulleroid derivatives with unusually high stability. Complete characterization of these derivatives is described including X-ray crystallography, 1H NMR, 13C NMR, HMQC, UV-visible, HPLC, MALDI-MS, and electrochemistry. D

2、ensity 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、3NC80,Olena Lukoyanova, Claudia M. Cardona, Jose Rivera, Leyda Z. Lugo-Morales, Christopher J. Chancellor, Marilyn M. Olmstead, Antonio Rodrguez-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,Properties of C60,Six-membered ring : 20 Fi

4、ve-membered ring : 12 5,6 bonds : 60(bond length : 1.45) 6,6 bonds : 30 (bond length : 1.38) Averge diameter : 7.1 ,http:/nano.nchc.org.tw/dictionary/c60.html,4,Electrochemical Detection of C606-,Echegoyen. L. et. al. J. Am. Chem. Soc. 1992, 114, 3978-3980.,5,13C NMR Spectrum of C60 in C6D6,Jingchen

5、g H ,et al ; J. Phys. Chem. B 2006, 110, 68-74,6,Mass Spectrum of C60,Mehlig.K ,at al ; J. Chem. Phys., 2003,119,5591-5600,7,Properties of C80,Six-membered ring : 30 Five-membered ring : 12 5,6 bonds : 60 6,6 bonds :60 Averge diameter : 8.2 ,http:/ Metallofullerene ( EMF ),Stevenson, S.; et al. Natu

6、re 1999, 401, 55-57,Sc3NC80,Shinohara, H.; et al. Bioconjugate Chem. 2001, 12, 510-514,9,Synthesis of Y3N(N-ethylpyrrolidino-C80),Echegoyen, L.et.al; J. Am. Chem. Soc. 2005, 127, 10448-10453,5.6&6,6,Y3N,Diels-Alder cycloadduct,10,5,6 and 6,6 Junction for Cycloaddition,Echegoyen, L.; et al. Angew. Ch

7、em., Int. Ed. 2006, 45, 8176-8180,5,6,6,6,5,6,6,6,11,Interconversion of 6,6 to 5,6,Y3Npyrrolidino-C80,Echegoyen, L.; et al. Angew. Chem., Int. Ed. 2006, 45, 8176-8180,6,6,5,6,12,Bingel-Hirsch Reaction,http:/en.wikipedia.org/wiki/Image:Bingel_reaction_mechanism.gif,13,Retro-Cyclopropanation Reaction,

8、Echegoyen, L,et al ; Eur. J. Org. Chem. 2004,2299-2316.,14,Synthesis Bingel-Hirsch Adducts,1, Y3NC80-C(CO2Et)2. Yield 85%,2, Y3NC80-C(CO2CH2Ph)2. Yield 76%,( ODCB ),15,Cyclic Voltammetry of Compound 1,16,MALDI-MS Spectrum of Comound 1,1, Y3NC80-C(CO2Et)2, after chemical reduction with sodium metal i

9、n THF. Matrix-Assisted Laser Desorption Ionization .,17,Y3NC80-C(CO2CH2Ph)2,Sc3NC80 C1-C9 1.421 .,C1-C9 : 2.30 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

10、side five-membered ring containing C9 on the right side.,C1,C9,19,Three Orientations of the Y3N Units in 2,0.7 occupancy 0.21 occupancy 0.09 occupancy,90 K,20,1H NMR Spectra of 2,dd,d,H,H,21,Heteronuclear Multiple Quantum Coherence (HMQC) and Heteronuclear Multiple Bond Coherence (HMBC) are 2-dimens

11、ional 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).,22,13C NMR Spectrum,downfield,23,HMQC,Heteronuclear Multiple Quantum Coherence (HMQC)

12、 is selective for direct C-H coupling .,http:/www.chemistry.msu.edu/facilities/nmr/HMQC.html,13C NMR,1H NMR,24,HMQC Spectrum,13C NMR,1H NMR,25,UV-Visible Spectra,26,Relative Position of the Y3N Unit in Y3NC80-C(CO2CH3)2,a BE =EY3NC80-C(CO2CH3)2 - EY3NC80 -EC(COOCH3)2. b The calculations were using D

13、FT with B3PW91 / 6-311G(2d,p),Bond Energiesaab (in kcal mol-1),27,Bonding Energy for the most Stable 2 6,6 Isomers,28,Distances of the 6,6-Methano Derivative of Y3NC80,a B3PW91 / 6-311G(2d,p),29,Representations of Functionalized La2C80,DFT Calaulation,a B3PW91 / 6-311G(2d,p) b multipole derived char

14、ge method(MDC-q),30,Representations of Functionalized Sc2C80,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 endoh

15、edral 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 experi

16、mental and theoretical characterization and analysis of the malonate monoadducts of Y3NC80, 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, 6928-6935,34,DFT,35,Stevenson, S.; et al. Nature 1999, 401, 55-57,