Interaction of the Buchwald Seven-Membered Zirconacyclocumulene
Complex with Carbonyl Compounds
Posted on 2019-06-26 - 15:37
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 Me3SiCC–CCSiMe3 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-Me3SiCC(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
CC 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)CC(CCSiMe3)]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.
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Burlakov, Vladimir
V.; Andreev, Maxim V.; Bogdanov, Vyacheslav S.; Smol’yakov, Alexander F.; Minacheva, Mariya Kh.; Shur, Vladimir B. (2019). Interaction of the Buchwald Seven-Membered Zirconacyclocumulene
Complex with Carbonyl Compounds. ACS Publications. Collection. https://doi.org/10.1021/acs.organomet.9b00190