Fullerenes Encapsulating an Ytterbium Atom: Molecular Structures and Chemical Properties

Endohedral metallofullerenes (EMFs) are novel hybrid molecules with metal atoms or metal clusters being encapsulated inside fullerene cages.^[1] In spite that the EMFs encapsulating divalent metal ions are less produced than other species, a series of mono-ytterbium have been successfully synthesized and isolated in our recent experiments. Their cage structures were systematically investigated with ¹³C NMR spectroscopy in combination with computational works.^[2] To seek insights into the metal location and metal-cage interactions in these Yb@C_2n (2n = 80, 82) compounds, their cocrystals with Ni^II(octaethylporphyrin) have been investigated with X-ray diffraction (XRD) crystallography.^[3]

More meaningfully, chemical properties of divalent EMFs were investigated for the first time with a carbene probe. The isolated derivatives were systematically characterized with a collection of theoretical and experimental techniques, including single crystal XRD crystallography. Unique interplays between the internal divalent metal ion and the addend have been observed.^[4]

References:

[1] X. Lu, L. Feng, T. Akasaka, S. Nagase, Chem. Soc. Rev. 2012, 41, 7723-7760.

[2] X. Lu, Z. Slanina, T. Akasaka, T. Tsuchiya, N. Mizorogi, S. Nagase, J. Am. Chem. Soc. 2010, 132, 5896-5905.

[3] (a) X. Lu, Y. Lian, C. M. Beavers, N. Mizorogi, Z. Slanina, S. Nagase, T. Akasaka, J. Am. Chem. Soc. 2011, 133, 10772-10775. (b) M. Suzuki, Z. Slanina, N. Mizorogi, X. Lu, S. Nagase, T. Akasaka, J. Am. Chem. Soc. 2012, 134, 18772–18778.

[4] (a)Y-P. Xie, M. Suzuki, W. Cai, N. Mizorogi, S. Nagase, T. Akasaka, X. Lu, Angew. Chem. Int. Ed. 2013, 52, 5142-5145. (b) W. Zhang, M. Suzuki, Y-P. Xie, L. P. Bao, W. T. Cai, Z. Slanina, S. Nagase, M. Xu, T. Akasaka, X. Lu, J. Am. Chem. Soc. 2013, 135, 12730-12735.