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Photochemical carbosilylation of Lu3N@Ih-C80 was performed using siliranes (silacyclopropanes) to afford the corresponding [5,6]- and [6,6]-adducts. Electrochemical studies indicated that the redox potentials of the carbosilylated derivatives were shifted cathodically in comparison with those of the [5,6]-pyrrolidino adducts. The electronic effect of the silirane addends on Lu3N@Ih-C80 was verified on the basis of density functional theory calculations. [ABSTRACT FROM AUTHOR]

We demonstrate that a finite-length (10,0) carbon nanotube (CNT) with twofullerene caps, namely D5(450)-C100, is an ideal prototype to study the mechanical responses of small CNTs upon endohedral metal doping. Encapsulation of a large La2C2 cluster inside D5(450)-C100 induces a 5% axial compression of the cage, as compared with the structure of La2@D5(450)-C100. Detailed crystallographic analyses reveal quantitively the flexibility of the [10]cyclacenesidewall segment and the rigidity of the pentagon-dominating caps for the first time. The internal C2-unit acts as a molecular spring that attracts the surrounding cage carbon atoms through strong interactions with the two moving lanthanum ions. This is the first crystallographic observation of the axial compression of CNTs caused by the internal stress, which enhances our knowledge about the structural deformation of novel carbon allotropes at the atomic level. [ABSTRACT FROM AUTHOR]

Thermal carbosilylation of endohedral dimetallofullerene La2@Ih-C80 with silirane (silacyclopropane) is reported herein for the first time. Two diastereomers of the carbosilylated La2@Ih-C80 have been isolated and characterized. The fascinating molecular structure of one diastereomer of the carbosilylated derivatives has been determined unambiguously using X-ray crystallographic analysis. Detailed characteristics of the molecular structures including their metal atom movements have also been revealed using NMR spectroscopic studies and computational calculations. Results revealed that two La atoms move dynamically inside the carbon sphere. Furthermore, electrochemical study has demonstrated that carbosilylation is effective to fine-tune the La2@Ih-C80 electronic properties. [ABSTRACT FROM AUTHOR]

Highly regioselective 1,3-dipolar cycloaddition of 3,5-dichloro-2,4,6-trimethoxybenzonitrile oxide (1) to Sc3N@Ih-C80 or C60 affords the corresponding isoxazoline-ring-fused derivatives Sc3N@Ih-C80(C10H9O4NCl2) (2a) and C60(C10H9O4NCl2) (2b). 2a represents the first example of an endohedral metallofullerene derivative with an isoxazoline ring. Crystallographic and NMR spectroscopic studies reveal a [5,6]-bond addition pattern in 2a but a [6,6]-bond addition manner in 2b. [ABSTRACT FROM AUTHOR]

New types of λ6-sulfanenitrile–transition metal complexes, [MCl2(ndsdsd)] (1) and [M(ndsdsd)2]Cl2 (2) (M = Co(II), Ni(II), Cu(II)), were obtained by reacting MCl2 with bis[(nitrilo(diphenyl)-λ6-sulfanyl)](diphenyl)-λ6-sulfanediimide Ph2S(ᆖN–(Ph2)S≡N)2 (ndsdsd). The crystal structures of these complexes have been elucidated by X-ray crystallographic analysis. The results revealed that, in complexes 1 and 2, the two terminal nitrogen atoms chelate to the metal center to form an eight-membered sulfur–nitrogen ring. [Copyright &y& Elsevier]