Synthesis of Silylene-Bridged Endohedral Metallofullerene Lu3N@Ih-C80

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• 作者：Kumiko Sato ; Masahiro Kako ; Mitsuaki Suzuki ; Naomi Mizorogi ; Takahiro Tsuchiya ; Marilyn M. Olmstead ; Alan L. Balch ; Takeshi Akasaka ; Shigeru Nagase
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：September 26, 2012
• 年：2012
• 卷：134
• 期：38
• 页码：16033-16039
• 全文大小：362K
• 年卷期：v.134,no.38(September 26, 2012)
• ISSN：1520-5126

文摘

Functionalization of endohedral metallofullerenes has been shown to differ depending on photochemical or thermal pathways. We report that Lu₃N@I_h-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鈥搉ear-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 I_h-C₈₀ cage. The electrochemical study reveals that the redox potentials of 1a and 1b are shifted cathodically compared to those of pristine Lu₃N@I_h-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.