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American Chemical Society, Inorganic Chemistry, 24(48), p. 11685-11690, 2009

DOI: 10.1021/ic9017147

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Selective Complexation and Reactivity of Metallic Nitride and OxoMetallic Fullerenes with Lewis Acids and Use as an Effective Purification Method

Journal article published in 2009 by Steven Stevenson ORCID, Mary A. Mackey, Jane E. Pickens, Melissa A. Stuart, Bridget S. Confait, J. Paige Phillips
This paper is available in a repository.
This paper is available in a repository.

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Abstract

Metallic nitride fullerenes (MNFs) and oxometallic fullerenes (OMFs) react quickly with an array of Lewis acids. Empty-cage fullerenes are largely unreactive under conditions used in this study. The reactivity order is Sc(4)O(2)@I(h)-C(80) > Sc(3)N@C(78) > Sc(3)N@C(68) > Sc(3)N@D(5h)-C(80) > Sc(3)N@I(h)-C(80). Manipulations of Lewis acids, molar ratios, and kinetic differences within the family of OMF and MNF metallofullerenes are demonstrated in a selective precipitation scheme, which can be used either alone for purifying Sc(3)N@I(h)-C(80) or combined with a final high-performance liquid chromatography pass for Sc(4)O(2)@I(h)-C(80), Sc(3)N@D(5h)-C(80), Sc(3)N@C(68), or Sc(3)N@C(78). The purification process is scalable. Analysis of the experimental rate constants versus electrochemical band gap explains the order of reactivity among the OMFs and MNFs.