title: Synthesis of silylene-bridged endohedral metallofullerene Lu3N@I(h)-C80.
abstract: Functionalization of endohedral metallofullerenes has been shown to differ depending on photochemical or thermal pathways. We report that Lu(3)N@I(h)-C(80) 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 I(h)-C(80) cage. The electrochemical study reveals that the redox potentials of 1a and 1b are shifted cathodically compared to those of pristine Lu(3)N@I(h)-C(80) 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 Lu(3)N cluster.
authors.affiliation: Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, lbaraki 305-8577, Japan.
authors.forename: Kumiko
authors.initials: K
authors.lastname: Sato
authors.forename: Masahiro
authors.initials: M
authors.lastname: Kako
authors.forename: Mitsuaki
authors.initials: M
authors.lastname: Suzuki
authors.forename: Naomi
authors.initials: N
authors.lastname: Mizorogi
authors.forename: Takahiro
authors.initials: T
authors.lastname: Tsuchiya
authors.forename: Marilyn M
authors.initials: MM
authors.lastname: Olmstead
authors.forename: Alan L
authors.initials: AL
authors.lastname: Balch
authors.forename: Takeshi
authors.initials: T
authors.lastname: Akasaka
authors.forename: Shigeru
authors.initials: S
authors.lastname: Nagase
mesh_terms: D002851:Chromatography, High Pressure Liquid; D018360:Crystallography, X-Ray; D037741:Fullerenes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008958:Models, Molecular; D019265:Spectroscopy, Near-Infrared
chemical_list: D037741:Fullerenes