Abstract
The reaction of Cp 2Ti(Me 3SiC 2SiMe 3) ( 1) with terminal disubstituted α,ω-diynes RC≡C(CH 2) n C≡CR affords, after substitution of Me 3SiC 2SiMe 3, bicyclic titanacyclopentadienes via intramolecular cyclization. The stability of the obtained products 2, 3 and 5 is determined by the spacer length ( n = 2, 4, 5, 6). The four-membered ring derivatives ( n = 2) 2a and 2b were obtained in good yield. In the case of n = 4 the bicyclic six-membered ring 3 was formed at first, which rearranges to a stable tricyclic η 4: η 3-dihydroindenyl-Ti complex 4 by Cp cleavage and intramolecular CC coupling. Complex 4 was characterized by X-ray structure analysis and NMR spectroscopy. An increase of spacer length ( n > 4) provides indefinable secondary and decomposition products.
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