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The reactions of Mn,(CO),NCMe (1) with the alkynes M e C S X (X = OEt, NMe,) have ylelded the substituted bridging vinylidene complexes Mn,(CO),[p-C=C(Me)C=O(X)] (2a, X = E t ; 2b, X = NMe, ) in 39% and 10% yields, respectively, by a rearrangement of the alkyne accompanied by a CO insertion. Compound 2b also adds 1 equiv of MeC--VNMe, to form the complex Mn,(CO), Summary: Organoianthanide complexes of the type Cp' ,LnR (Cp' = $-Me, C, ; Ln = La, Nd, Sm, Y, Lu; R = H, CH(SiMe3),), Me,Si Cp",LnR (Cp" = q5-Me,C,; Ln = Nd; R = CH(SIMe3),), Cp' ,Sm, and Cp' ,Sm(THF), catatyze the rapid dehydrogenative oligomerization of PhSi H,.Kinetic and mechanistic arguments exclude the importance of metakentered redox processes in the catalytic cycle and support instead "four-center'' "heterolytic" bond-scission/bond-forming sequences.

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