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Reactivity of Permethylzirconocene and Permethyltitanocene toward Disubstituted 1,3-Butadiynes:  η4- vs η2-Complexation or C−C Coupling with the Permethyltitanocene

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posted on 1999-08-31, 00:00 authored by Paul-Michael Pellny, Frank G. Kirchbauer, Vladimir V. Burlakov, Wolfgang Baumann, Anke Spannenberg, Uwe Rosenthal
This paper describes the reactivity of permethylzirconocene and permethyltitanocene toward different 1,3-butadiynes. A pointed dependence on the metals and the diyne substituents was found. Unusual, but still stable, five-membered zirconacyclocumulenes (η4-diyne complexes, zirconacyclopenta-2,3,4-trienes) Cp*2Zr(η4-1,2,3,4-RC4R), R = Ph and SiMe3, were prepared using two new and effective synthetic routes. One starts with the permethylzirconocene bisacetylides Cp*2Zr(C⋮CR)2, R = Ph (1a), SiMe3 (1b), which rearrange in sunlight to form the stable five-membered zirconacyclocumulenes Cp*2Zr(η4-1,2,3,4-RC4R), R = Ph (2a), SiMe3 (2b). The alternative route to 2a and 2b is the reduction of Cp*2ZrCl2 with Mg in the presence of the adequate disubstituted butadiynes RC⋮C−C⋮CR. Both methods failed to produce the analogous titanacyclocumulenes, which seemed extremely unstable. Nevertheless, we were able to obtain distinct products employing the reduction pathway with permethyltitanocene. For R = SiMe3, the novel titanacyclopropene (η2-complex) Cp*2Ti(η2-1,2-Me3SiC2C⋮CSiMe3) (3) was isolated. For R = Ph, an activation of both pentamethylcyclopentadienyl ligands was observed resulting in the complex [η5-C5Me4−(CH2)−]Ti[−C(CHPh)C(CHPh)CH25-C5Me4] (4). The reaction of 4 with carbon dioxide led to the Cp*-substituted titanafuranone Cp*Ti[−OC(O)C(Ph)C(−)C(CHPh)CH25-C5Me4] (5). The zirconacyclocumulene 2b surprisingly inserted two molecules of CO2 to give the unprecedented cumulenic dicarboxylate Cp*2Zr [−OC(O)C(SiMe3)CCC(SiMe3)C(O)O−] (6). The η2-complex 3 (titanacyclopropene) took up one molecule of carbon dioxide to afford the titanafuranone Cp*2Ti[OC(O)C(SiMe3)C(C⋮CSiMe3)−] (7).

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