Reactions of fullerenes with reactive methylene organophosphorus reagents: efficient synthesis of organophosphorus group substituted C60 and C70 derivatives.
Treatment of C70 with cycloalkylaminomethylenebisphosphonates in the presence of NaH gave corresponding C70 dimers 1 in good yield, while the methanofullerenes, C70>CH(PO3Et2) (3) and C70>C(PO3Et2)2 (4) or C60>CH(PO3Et2) (5) and C60>C(PO3Et2)2 (6), were obtained, respectively, by the reaction of C70 or C60 with tetraethyl methylenediphosphonate in the presence of NaH. Diethyl cyanomethylphosphonate reacted with C60 or C70 under similar conditions to afford C60>C(PO3Et2)CN (7) and C70>C(PO3Et2)CN (8). Furthermore, the presence of weak electronic interactions between two fullerene cages of fullerene dimers was demonstrated by cyclic voltammetry. A radical mechanism was proposed for the formation of the fullerene derivatives on the basis of the ESR studies.
Yin
Juan-Juan
JJ
Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China. yinjj@mail.sioc.ac.cn
Jin
Li-Mei
LM
Liu
Rui-Li
RL
Li
Qing-Nuan
QN
Fan
Chun-Hai
CH
Li
Yan
Y
Li
Wen-Xin
WX
Chen
Qing-Yun
QY
D004578:Electron Spin Resonance Spectroscopy; D037741:Fullerenes / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D012680:Sensitivity and Specificity; D013237:Stereoisomerism
D037741:Fullerenes; D009943:Organophosphorus Compounds