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Based on the observation that the alkylidyne bridged cluster HFeCo 2 (CO) 9 (μ 3 -C—CH 3 ) spontaneously loses H 2  to form the vinylidene bridged cluster FeCo 2 (CO) 9 (μ 3 -C=CH 2 ), the interconversions between these types of ligands on mixed trinuclear clusters were investigated. It was found that in all cases clusters of the type HM 3 μ 3 -C—CH 2 R) could be transformed into clusters of the type M 3 (μ 3 -C=CHR); for M 3  = FeCo 2 , FeCoMo, RuCoMo, RuCoW, OsCoMo, OsCoW; for R = H and in one case CH 3 ; for dehydrogenation by thermolysis and in one case H + /H -  elimination. Conversely, hydrogenation of the vinylidene bridged clusters to the alkylidyne bridged clusters was only possible for the FeCoMo, RuCoMo, and RuCoW systems, for the unsubstituted C=CH 2  ligand, and for elemental hydrogen as the reagent. Together with previous observations this leads to the conclusion that among the interconvertible alkyne, vinylidene, and alkylidyne ligands the vinylidene unit represents the most stable entity on trinuclear clusters.

zeitschrift für naturforschung b

Umwandlungen zwischen Vinyliden- und Alkylidin-verbrückten Dreikernclustern / Interconversions between Vinylidene and Alkylidyne Bridged Trinuclear Clusters