Radical coupling reaction of paramagnetic endohedral metallofullerene La@C82.
The thermal reaction of La@C(82)(C(2v)) with 3-triphenylmethyl-5-oxazolidinone (1) in toluene affords benzyl monoadducts La@C(82)(C(2v))(CH(2)C(6)H(5)) (2a-2d). The same monoadducts are also obtained by the photoirradiation of La@C(82)(C(2v)) in toluene without the existence of 1. These reactions are applicable to paramagnetic metallofullerenes, such as La@C(82)(C(s)) and Ce@C(82)(C(2v)). The photoirradiation of La@C(82)(C(2v)) in 1,2-dichlorobenzene in the presence of alpha,alpha,2,4-tetrachlorotoluene also affords the monoadducts La@C(82)(C(2v))(CHClC(6)H(3)Cl(2)) (3a-3d). The monoadducts are fully characterized by spectroscopic analyses. Single-crystal X-ray structure analysis for 3d reveals the unique structure. Theoretical calculations show that the cage carbons having high spin densities are selectively attacked by radical species to form the monoadducts linked by a carbon-carbon single bond. The thermal reaction of La@C(82)(C(2v)) with 1 in benzene affords metallofulleropyrrolidine La@C(82)(C(2v))(C(2)H(4)NCPh(3)) (5), unlike the reaction in toluene.
Takano
Yuta
Y
Center for Tsukuba Advanced Research Alliance, University of Tsukuba, Tsukuba, Ibaraki 305-8577, Japan.
Yomogida
Akinori
A
Nikawa
Hidefumi
H
Yamada
Michio
M
Wakahara
Takatsugu
T
Tsuchiya
Takahiro
T
Ishitsuka
Midori O
MO
Maeda
Yutaka
Y
Akasaka
Takeshi
T
Kato
Tatsuhisa
T
Slanina
Zdenek
Z
Mizorogi
Naomi
N
Nagase
Shigeru
S
D001554:Benzene / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000737:chemistry; D037741:Fullerenes / Q000737:chemistry* / Q000302:isolation & purification; D007811:Lanthanum / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D012997:Solvents; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013055:Spectrophotometry, Infrared
D005609:Free Radicals; D037741:Fullerenes; D012997:Solvents; D007811:Lanthanum; D001554:Benzene