NICKELOCENE CHEMISTRY .2. NEW METHYLIDYNE TRINICKEL CLUSTER COMPOUNDS

The new methylidene trinickel cluster complexes, [RCNi3(η5-C5H53] (R CMe3 or SiMe3) and [Me3SiCNi3(η5-C5H5)2(η5-C5H4CH2SiMe3)] have been isolated in low yield from reactions between nickelocene and the corresponding alkyllithium reagents, RCH2Li. The compounds [RCNi3(η5-C5H5)3] (R Ph, CMe3 or SiMe3) have also been obtained by treatment of the σ-alkylnickel complexes [(η5-C5H5)Ni(CH2R)(PPh3)] with n-BuLi in the presence of an excess of nickelocene, but under similar conditions [(η5-C5H5)Ni(CH2C1OH7-2)-(PPh3)] (where C1OH7-2 2-naphthyl) failed to give [2-C1OH7CNi3(η5-C5H5)3]. The attempted synthesis of [(η5-C5H5)Ni(CH2CCH)(PPh3)] from [(η5-C5H5)-NiBr(PPh3)] and CHCCH2MgBr gave only [(η5-C5H5)Ni(CCMe)(PPh3)] by an unusual rearrangement reaction. © 1979.