The reactivity of the (?5-C5Me5)3Ln lanthanide complexes (Ln = La-Nd, Sm, Y) with THF, nitriles, and isocyanides has been examined and compared to that of (?5-C5Me5)3U.   Four types of reactions are observed depending on the particular combination of metal and base:   formation of a mono-adduct, (?5-C5Me5)3ML, formation of a bis-adduct, (?5-C5Me5)3ML2, the first example of this type of complex, insertion into a M-(C5Me5) bond, and cleavage to form cyanide products.  The reactivity trends observed will be analyzed in terms of metal size and 4f vs 5f electron configuration.   The isolation of (?5-C5Me5)3Ln(NCCMe3)2 and (?5-C5Me5)3Ln(CNCMe3)2 complexes shows that the limits of steric crowding in organometallic metallocene complexes are still expanding.

Reactivity of sterically crowded lanthanide and uranium (η5-C5Me5)3M complexes with Lewis Bases: Isolation of the first (η5-C5Me5)3ML2 complexes

239th National Meeting (2010)

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