Journal of the American Chemical Society, Vol.136, No.50, 17537-17546, 2014
Unprecedented Chemical Reactivity of a Paramagnetic Endohedral Metallofullerene La@C-5-C-82 that Leads Hydrogen Addition in the 1,3-Dipolar Cycloaddition Reaction
Synthesizing unprecedented diamagnetic adducts of an endohedral metallofullerene was achieved by using 1,3-dipolar cycloaddition reaction of paramagnetic La@C-5-C-82 with a simultaneous hydrogen addition. The selective formation of two main products, La@C-5-C82HCMe2NMeCHPh (2a and 2b), was first detected by HPLC analysis and MALDI-TOF mass spectrometry. 2a and 2b-O, which was readily formed by the oxidation of 2b, were isolated by multistep HPLC separation and were fully characterized by spectroscopic methods, including 1D and 2D-NMR, UVvis-NIR measurements and electrochemistry. The hydrogen atom was found to be connected to the fullerene cage directly in the case of 2a, and the redox behavior indicated that the CH bond can still be readily oxidized. The reaction mechanism and the molecular structures of 2a and 2b were reasonably proposed by the interplay between experimental observations and DFT calculations. The feasible order of the reaction process would involve a 1,3-dipolar cycloaddition followed by the hydrogen addition through a radical pathway. It is concluded that the characteristic electronic properties and molecular structure of La@C-5-C-82 resulted in a site-selective reaction, which afforded a unique chemical derivative of an endohedral metallofullerene in high yields. Derivative 2a constitutes the first endohedral metallofullerene where the direct linking of a hydrogen atom has been structurally proven.