Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2

The reactions of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 (1) and Fe{(μ-O2CC5H4)(μ-H)Os3(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 O atom of the bridging carboxylate group, and oxidative degradation of the complex. At low concentrations, CF3SO3H protonates the O atom of the bridging carboxylate group, while at high concentrations, degradation of the complex takes place. The reaction of complex 2with either CF3COOH or low concentrations of CF3SO3H results in successive elimination of two [(μ-H)Os3(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{(μ-O2CC5H4)(μ-H)2Os3(CO)10}2]2+ dication. The Friedel—Crafts acylation of 1 takes place only when a large excess of AcCl and AlCl3 is used to give two new complexes, (μ-H)Os3(μ-O2CC5H4FeC5H4C(O)CH3)(CO)10 and (μ-H)Os3(μ-O2CC5H3C(O)CH3FeCp)(CO)10 in a 2 : 1 ratio.