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Pure Appl. Chem., 2001, Vol. 73, No. 2, pp. 287-289

New methods for the synthesis of transition-metal fullerene complexes

David M. Thompson*, Jason McLeod and Michael C. Baird

Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada

Abstract: Buckminsterfullerene, C60, is readily reduced on exposure to solutions of strongly reducing transition-metal carbonylate anions to give the radical anion fulleride C60- and the corresponding highly reactive, 17-electron neutral compounds. Three secondary reaction paths have been identified, depending on the nature of the reactants and the reaction conditions. (1) With Na+ and PPN+ salts of [Mn (CO) 5]-, thermal substitution of a CO on the metal radical by the C60-results in formation of the anionic, h2-fullerene complex [Mn (C60) (CO) 4]- . (2) With salts of [Co (CO) 4]-, the thermal reaction results in formation of a novel transition-metal fulleride NaCoC60 while (3) with Na[CpFe (CO) 2] and [CpM (CO) 3]- (M = Mo, W) , the 17-electron intermediates couple to form the 18-electron dimers, [CpFe (CO) 2]2 and [CpM (CO) 3]2. In contrast, photochemical reactions of C60 with salts of [Mn (CO) 5]-, [Co (CO) 4]-, and [CpM (CO) 3]- result in excellent yields of the complexes [Mn (C60) (CO) 4]- , [Co (C60) (CO) 3]- and [CpM (C60) (CO) 2]- , respectively; analogous complexes of C70 may be made similarly. The new complexes have been characterized crystallographically, by IR, 13C NMR, and/or Raman spectroscopy and by electrospray mass spectrometry.