RESUMO
This overview explains some new aspects of chemical functionalization of endohedral metallofullerenes (EMFs) that have been unveiled in recent years. After differences in chemical reactivity between EMFs and the corresponding empty fullerenes are discussed, cage-opening reactions of EMFs are examined. Then, the selective bisfunctionalization of EMFs is explained. Finally, single-bonding derivatization of EMFs is addressed. The diversity and applicability of the chemical functionalization of endohedral metallofullerenes are presented to readers worldwide.
Assuntos
Fulerenos/química , Carbono/química , Reação de Cicloadição , Elementos da Série dos Lantanídeos/química , Modelos Químicos , Teoria QuânticaRESUMO
Bis-functionalization of endohedral metallofullerene La(2)@C(80) by carbene addition is reported herein. Adducts were characterized using spectroscopic and single-crystal X-ray structure analyses. Crystallographic data for bisadduct La(2)@C(80)(CClPh)Ad (3, Ad = adamantylidene) revealed that both carbene additions occur at the 6,6-bond junction on the C(80) cage with ring cleavages and that La atoms are positioned collinearly with spiro carbons. It is noteworthy that the La-La distance in 3 is highly elongated by carbene bis-functionalization compared to the distance in pristine La(2)@C(80) and reported functionalized derivatives. The metal positions were confirmed through density functional calculations.
RESUMO
The photochemical reaction of M2@C80 (M = La and Ce) with 2-adamantane-2,3'-[3H]-diazirine (1) affords the corresponding adducts by carbene addition. The adducts were characterized by spectroscopic and single-crystal X-ray structure analyses. Crystallographic data for the adduct La2@C80(Ad) (2, Ad = adamantylidene) reveal that the two La atoms are collinear with the spiro carbon of the 6,6-open adduct. It is noteworthy that the La-La distance is highly elongated by the addition of carbene. Paramagnetic 13C NMR spectral analysis of the adduct Ce2@C80(Ad) (3) indicates that the two Ce atoms are also collinear with the spiro carbon at room temperature in solution. The unique metal positions were confirmed by density functional calculations.
RESUMO
We report here the results on single crystal X-ray crystallographic analysis of the Gd@C82 carbene adduct (Gd@C82(Ad), Ad = adamantylidene). The Gd atom in Gd@C82(Ad) is located at an off-centered position near a hexagonal ring in the C2v-C82 cage, as found for M@C82 (M = Sc and La) and La@C82(Ad). Theoretical calculation also confirms the position of the Gd atom in the X-ray crystal structure.
Assuntos
Adamantano/química , Fulerenos/química , Gadolínio/química , Compostos Organometálicos/química , Cristalografia por Raios X , Metano/análogos & derivados , Metano/química , Estrutura MolecularRESUMO
The photochemical reaction of La@C82(Cs) with 2-adamantane-2,3-[3H]-diazirine (1) affords the adduct 2 of La@C82(Cs) with adamantylidene (Ad:) in a high selectivity. The two isomers of La@C82(Cs)(Ad), 2a and 2b, are isolated by HPLC and characterized by electron spin resonance, mass, and UV-vis-near-infrared spectroscopies. The electronic properties of 2a and 2b are very similar to that of the pristine La@C82(Cs), suggesting that 2a and 2b retain the essential electronic and structural character of La@C82(Cs).
RESUMO
We report here the structural determination of the Sc3C82 molecule by 13C NMR spectroscopy and X-ray single-crystal structure analysis. From the present study, it is obvious that the structure of Sc3C82 is not Sc3@C82 but Sc3C2@C80.
Assuntos
Fulerenos/química , Escândio/química , Isótopos de Carbono , Cristalografia por Raios X , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Compostos Organometálicos/químicaRESUMO
C(60) acts as a mechanistic probe for the formation of carbene, diazo compound, and for the rearranged product via the excited state in the photolysis of 3-chloro-3-isopropyldiazirine and 3-chloro-3-chloromethyldiazirine. The carbene adds to C(60) to form methanofullerene, whereas the diazo compound adds to C(60) to form fulleroid. The olefin product arises as a result of the rearrangement in the excited state.
RESUMO
The thermal decomposition of phenylchlorodiazirine (1), phenyl-n-butyldiazirine (2), and 2-adamantane-2,3'-[3H]diazirine (3) has been studied in solution in the presence of C(60). The C(60) probe technique indicates that in the decomposition diazirine 1 yielded exclusively phenylchlorocarbene, diazirine 2 yielded mainly a diazo intermediate, and diazirine 3 yielded a mixture of carbene and diazo compound. In the case of diazirine 2, 13% of (E)-1-phenyl-1-pentene resulted from the direct thermal rearrangement of diazirine without the participation of a carbene. As well, the thermal decomposition of these diazirines has been studied theoretically with ab initio and density functional methods. The experimental results are broadly in agreement with the theoretical predictions. The calculations further indicate that the rebound reaction between carbene and molecular nitrogen leading to the formation of a diazo intermediate is an important reaction in the gas-phase decomposition of diazirine.
RESUMO
The photochemical reaction of La@C82 with 2-adamantane-2,3-[3H]-diazirine affords adduct 2, La@C82(Ad), in a quantitative and highly selective manner. The structure of compound 2 is confirmed by ESR, MS, and UV-vis-NIR spectroscopies, and the first X-ray crystallographic characterization of an endohedral monometallofullerene derivative is reported.