RESUMO
Herein, we report the preparation, purification, and characterization of a mixed trimetallic nitride endohedral metallofullerene, CeSc(2)N@C(80). Single-crystal X-ray diffraction shows that CeSc(2)N@C(80) consists of a four-atom asymmetric top (CeSc(2)N) inside a C(80) (I(h)()) carbon cage. Unlike the situation in most endohedrals of the M(3)N@C(2)(n)() type, the nitride ion is not located at the center of the carbon cage but is offset by 0.36 A in order to accommodate the large Ce(III) ion. The cage carbon atoms near the endohedral Ce and Sc atoms exhibit significantly larger pyramidal angles than the other carbon atoms on the C(80) cage. Surprisingly, at ambient temperature, the (13)C NMR spectrum exhibits isotropic motional averaging yielding only two signals (3 to 1 intensity ratio) for the icosahedral C(80) cage carbons. At the same temperature, the (45)Sc NMR exhibits a relatively narrow, symmetric signal (2700 Hz) with a small temperature-dependent Curie shift. A rotation energy barrier (E(a) = 79 meV) was derived from the (45)Sc NMR line-width analysis. Finally, the XPS spectrum for CeSc(2)N@C(80) confirms a +3 oxidation state for cerium, Ce(3+)(4f(1)5d(0)). This oxidation state and the Curie shift are consistent with a weakly paramagnetic system with a single buried f electron spin.
Assuntos
Cério/química , Fulerenos/química , Espectroscopia de Ressonância Magnética/métodos , Escândio/química , Cério/isolamento & purificação , Cristalografia por Raios X , Elétrons , Fulerenos/isolamento & purificação , Modelos Moleculares , Escândio/isolamento & purificação , Sensibilidade e Especificidade , Espectrofotometria/métodos , Espectrofotometria Ultravioleta/métodos , Análise Espectral , Raios XRESUMO
The pure I(h) isomer of Sc3N@C80 was allowed to react with N-triphenylmethyl-5-oxazolidinone via the corresponding azomethine ylide. The reaction results in the formation of two monoadducts; one (1b) is the kinetic product, and the other (1a) is thermodynamically more stable. Small amounts of the bisadducts were also formed. The structure of the thermodynamic monoadduct 1a was shown conclusively by NMR spectroscopy and X-ray crystallography to result from addition across the 5,6-ring junction. The kinetic product 1b was demonstrated to be the 6,6-ring juncture adduct on the basis of NMR experiments and X-ray crystallography. In refluxing chlorobenzene pure 1b was converted to the more thermodynamically stable 1a isomer. These N-tritylpyrrolidino derivatives are potentially useful precursor compounds for further derivatization for various applications.
RESUMO
New pyrrolidino derivatives of both diamagnetic and paramagnetic trimetallic nitride templated endohedral metallofullerenes were synthesized by the Prato reaction, isolated and characterized by means of MALDI-TOF MS, NMR and UV-vis spectroscopies.
Assuntos
Fulerenos/química , Metais/química , Pirrolidinonas/síntese química , Magnetismo , Pirrolidinonas/química , Análise EspectralRESUMO
Bioassay-guided fractionation of the EtOAc extract of the twigs of Garcinia macrophylla from Suriname produced the known benzophenone, guttiferone A (1), and a new guttiferone analogue, guttiferone G (2). Friedelin was also isolated. The structures of compounds 1 and 2 were elucidated using 1D and 2D NMR spectroscopy. Compounds 1 and 2 were weakly cytotoxic in the A2780 human ovarian cell line, with IC (50) values of 6.8 and 8.0 microg/mL, respectively.