R. Beckhaus , J. Oster, J. Sang, I. Strauß M. Wagner
Synlett 1997, 3, 241-249
Different rotameres of 1-Alkenyl complexes of early transition metals lead to the selective formation of diene complexes, metallacyclopentenes or vinylidene intermediates. In such a way the titaniumvinylidene species [Cp*2Ti=C=CH2] (1) can easily be generated from methylenetitanacyclobutane Cp*2TiC(=CH2)CH2CH2 (2), obtained via a Cp*2Ti(CH=CH2)2 intermediate (3) in quantitative yield, or by a-H-elimination of methane from the vinyl-methyl derivative, Cp*2Ti(CH=CH2)CH3 (4). The systems 2 - 1 or 4 - 1 can be used in a great number of different organometallic reactions. Of considerable interest are syntheses of cycloaddition products, by trapping 1 with cumulenes, transition metal carbonyls, nitriles, phosphaalkynes and alkynes. The obtained products are of high thermal stability due to the stabilization effect of the a-exo-methylene group, the formation of stronger Csp2-Csp2-bonds in the four membered rings and the lowered electrophilicity of the titanium center caused by the strongly basic Cp*-ligands. With oxygen containing cumulenes and heterocumulenes, monomeric metallaoxetanes exhibiting a planar ring geometry are obtained for the first time. Due to its reactivity in solution the metallaoxetanes can be divided in classical (forming Ti=O) and nonclassical oxetanes (forming Ti=C). Reactions of 1 with transition metal carbonyls lead to the formation of metallaoxetanes exhibiting a nonclassical behavior. These nonclassical oxetanes rearrange into five-membered cyclic Fischer-carbene complexes upon heating. Starting from cycloaddition products of 1 which exhibit titanacyclobutane or titanacyclobutene structures, ring-enlargement reactions could be achieved by using carbon monoxide, nitriles or isonitriles. The formation of trans-polyacetylene is observed in reaction of 1 with an excess of acetylene. An intermolecular carbene-carbene coupling reaction of a Fischer- and a Schrock-carbene ligand by coupling the vinylidene fragment in 1 [Cp*2Ti=C=CH2] with the methoxyethylidene moiety of the chromium complex (CO)5Cr=C(OMe)Me is described. A stabilization of 1 is achieved by complexation with unsaturated copper and gold complexes, forming dinuclear s,s-m-vinylidene complexes.