Spectroscopic Evidence for Anionic Coordination Complexes of the Transition Metals with C70 and the Higher Fullerenes C76, C78, C82, C84, C86, C90, and C92 |
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| Authors: | David M Thompson John H Brownie Michael C Baird |
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| Affiliation: |
a Department of Chemistry, Queen's University, Kingston, Ontario, Canada |
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| Abstract: | The carbonylate anions M(CO)5]- (M = Mn, Re), Co(CO)4]-, CpFe(CO)2]-, and CpM(CO)3]- (M = Mo, W) react with C70 via single electron transfer processes to give, respectively, the corresponding 17-electron, metal-centered radicals Co(CO)4, M(CO)5 (M = Mn, Re), CpFe(CO)2, and CpM(CO)3 (M = Mo, W) in addition to the radical anion C70-. In secondary thermal or photochemical processes, the metal-centered radicals Co(CO)4 and M(CO)5 (M = Mn, Re) combine with the C70- to form the new η2-C70 complexes Co(CO)3(η2-C70)]- and M(CO)4(η2-C70)]-. However, the metal-centered radicals CpM(CO)3 (M = Mo, W) require photolysis to react with C70- to form CpM(CO)2(η2-C70)]-, whereas neither thermolysis nor photolysis induces reaction between CpFe(CO)2 and C70-. The photochemical reaction of Mn(CO)5]- with a mixture of higher fullerenes known to contain at least C76, C78, C84, C86, and C90 resulted similarly in the formation of the higher fullerene complexes Mn(CO)4(η2-Cn)]- (n = 76, 78, 80, 82, 84, 86, 88, 90, 92, 96, and 98), all identified using electrospray mass spectrometry. |
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| Keywords: | Fullerenes Manganese Rhenium Cobalt Molybdenum Tungsten |
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