Synthesis of Silylene-Bridged Endohedral Metallofullerene Lu3N@Ih-C80
2012
Satō, Kumiko | Kako, Masahiro | Suzuki, Mitsuaki | Mizorogi, Naomi | Tsuchiya, Takahiro | Olmstead, Marilyn M. | Balch, Alan L. | Akasaka, Takeshi | Nagase, Shigeru
Functionalization of endohedral metallofullerenes has been shown to differ depending on photochemical or thermal pathways. We report that Lu₃N@Iₕ-C₈₀ reacts with thermally generated bis(2,6-diethylphenyl)silylene with high selectivity and forms monosilylated derivative 1b. Unexpectedly, 1b undergoes photochemical conversion to afford isomer 1a under ambient light. These adducts were characterized using NMR, visible–near-IR spectroscopy, and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. Single-crystal X-ray structure determination of 1a reveals a rare example of an open 1,2-adduct at the [5,6]-ring junction of the Iₕ-C₈₀ cage. The electrochemical study reveals that the redox potentials of 1a and 1b are shifted cathodically compared to those of pristine Lu₃N@Iₕ-C₈₀ and that monosilylation is effective to fine-tune the electronic properties of endohedral metallofullerenes as well as empty fullerenes. Density functional theory calculations were also performed, which provide a theoretical basis for the structures and the behavior of the encapsulated Lu₃N cluster.
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