Interaction of the Buchwald Seven-Membered Zirconacyclocumulene Complex with Carbonyl CompoundsстатьяИсследовательская статья
Статья опубликована в высокорейтинговом журнале
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Аннотация:The interaction of the Buchwald seven-membered zirconacyclocumulene Cp2Zr[η4-Me3SiC4(SiMe3)–C(C2SiMe3)=CSiMe3] (1) with a 2-fold excess of benzophenone in toluene at 100 °C for 20 h results in the formation of Me3SiC≡C–C≡CSiMe3 and a nine-membered dioxazirconacycle Cp2Zr[η2-OC(Ph)2C(SiMe3)C2C(SiMe3)C(Ph)2O] (5) containing [3]cumulene group in the ring. Analogous metallacycle (6) is formed on heating of 1 with fluorenone in toluene at 100 °C. A treatment of 5 with HCl in dioxane at 20 °C affords Cp2ZrCl2 and cis-[3]cumulenic diol Ph2(HO)C(Me3Si)CC2C(SiMe3)C(OH)Ph2 (7) in 85% yield. The reaction of 1 with benzil (PhCO)2 at 80 °C in benzene proceeds differently than with benzophenone and fluorenone. In this case, a nine-membered dioxazirconacycle Cp2Zr[η2-Me3SiC═C(C2SiMe3)–C(SiMe3)═C(C2SiMe3)OC(Ph)═C(Ph)O] (10) is produced. The nature of products formed in the interaction of 1 with acenaphthenequinone proved to be temperature dependent. Thus, on carrying out the reaction at 20 °C, an 11-membered trioxazirconacycle (11) containing three C═C bonds in the ring was isolated from the mixture, whereas at 80 °C the reaction gave a ten-membered tetraoxadizirconacycle (12) and octasubstituted cyclooctatetraene [(Me3Si)C═C(C≡CSiMe3)]4 (13). The structures of 5–7 and 10–13 have been determined by X-ray diffraction. The mechanism of the reactions found is discussed.