| The thermal and photochemical reactions of the salts of transition metal carbonylates: A[Mn(CO)5], A[Co(CO)4], A[CpMo(CO) 3] (Cp = η5-C5H5), A[CpW(CO) 3], A[CpFe(CO)2] and Na[Re(CO)5] (A = Na +, A = PPN+ = [(PPh3)2N] +) with fullerenes (C60 and C70), have been studied.; It is believed that all of these reactions involve initial electron transfer from the transition metal carbonylate to the fullerene to generate a 17-electron metal radical and the fulleride radical monoanion. Subsequent metal radical dimerization competes with fulleride substitution for a carbonyl ligand leading to a mixture of (η2-fullerene)transition metal carbonylates, metal-metal dimer and the fulleride monoanion.; While the metal dimer and a salt of the fulleride monanion are among the products of the thermal reaction, under photochemical conditions, metal radical dimerization becomes a reversible process and under these conditions we are able to obtain high yields of salts of (η2-fullerene)transition metal carbonylates. The following (η2-fullerene)metal carbonylate salts have been observed and characterized by infrared spectroscopy, electrospray mass spectrometry and high resolution mass spectrometry: A[Mn(CO)4(η 2-C60)], A[Co(CO)3(η2-C 60)], A[CpMo(CO)2(C60)], A[CpW(CO)2(η 2-C60)] (A = Na+, PPN+); Na[Re(CO)4(η2-C60)], PPN[Mn(CO) 4(η2-C70)], PPN[Co(CO)3(η 2-C70)], PPN[CpMo(CO)2(η2-C 70)], PPN[CpW(CO)2(η2-C70)] and Na[Re(CO)4(η2-C70)]. A cursory examination of some the chemistry that the η2-C 60 complexes participate in has been made and it appears that the (η 2-fullerene)metal carbonylates are much less labile than other metal-C 60 complexes with respect to ligand substitution.; The reactions of PPN[Mn(CO)5] with a mixture of higher fullerenes have also been studied and species of the type [Mn(CO)4(η 2-fullerene)]− for many higher fullerenes have been studied by electrospray mass spectrometry suggesting that this chemistry may be applied to higher fullerenes.; The reactions of PPN[Co(CO)4] and PPN[Mn(CO)5] with graphitic soots rich in fullerenes have been demonstrated to result in the formation of (η2-fullerene)metal carbonylates. |
