Monomeric cyclopentadiene molybdenum oxides and their carbonyl precursors as epoxidation catalysts

Monomeric cyclopentadiene molybdenum oxides were among the first synthesized high oxidation state organometallics. However, their syntheses and applications have long been overshadowed by their rhenium(VII) congeners, in particular by (pentamethylcyclopentadienyl)trioxorhenium(VII) and methyltrioxorhenium(VII). Only during the last decade a renaissance of the cyclopentadienyl molybdenum oxides is starting. Both with respect to synthetic access ways and to applications as oxidation catalysts in homogeneous and heterogeneous phase the interest in cyclopentadienyl molybdenum oxides and their tricarbonyl precursors is increasing. This results from the usually time-easy and straightforward synthetic procedures leading to these compounds and their easy heterogenizability, both on mesoporous materials and in ionic liquids. The catalytic performance, especially in olefin epoxidation with tert-butylhydroperoxide being the oxidant is very good and the derivatization to reach taylor made catalysts seems to be much easier than in the case of the organorhenium oxides. Another advantage in comparison to the latter complexes is the possible presence of two organic functionalities, which can be independently modified, e.g. for heterogenization of the complexes and for the enhancing of their catalytic activity at the same time.

Monomeric cyclopentadiene molybdenum oxides are receiving increased interest both concerning their preparation and reaction chemistry and with regard to possible catalytic applications. The use of the title compounds as epoxidation catalysts in homogeneous phase and after immobilization has been examined in some detail and is also summarized here.Figure optionsDownload as PowerPoint slide