摘要:
The reactions of the heterometallic complexes (mu-H)OS3(mu-O2CC5H4FeCp)(CO)(10) (1) and Fe{(mu-O2CC5H4)(mu-H)Os-3(CO)(10)}(2) (2) with CF3COOH, CF3SO3H, and AcCl were studied. The reaction of 1 with CF3COOH involves interaction with the Cp ligands, protonation of the 0 atom of the bridging carboxylate group, and oxidative degradation of the complex. At low concentrations, CF3SO3H protonates the 0 atom of the bridging carboxylate group, while at high concentrations, degradation of the complex takes place. The reaction of complex 2 with either CF3COOH or low concentrations of CF3SO3H results in successive elimination of two [(mu-H)Os-3(CO)(10)] cluster fragments due to protonation of the O atoms of the carboxylate groups. In the case of high CF3SO3H concentrations, the Os-Os bonds of both cluster fragments of 2 are also protonated to give the [Fe{(mu-O2CC5H4)(mu-H)(2)Os-3(CO)(10))(2)](2+) dication. The Friedel-Crafts acylation of I takes place only when a large excess of AcCl and AlCl3 is used to give two new complexes, (mu-H)Os-3(mu-O2CC5H4FeC5H4C(O)CH3)(CO)(10) and (mu-H)Os-3(mu-O2CC5H3C(O)CH3FeCp)(CO)(10) in a 2 : 1 ratio.