Vinyl-acetamidination of in-situ generated Acetylenic Complexes of Zirconocenes. Thermal Isomerisation of Obtained Zirconabicycles

Авторы: Andreev Maxim V., Bogdanov Vyacheslav S., Aisin Rinat R., Smol’yakov Alexander F., Dolgushin Fedor M., Burlakov Vladimir V.
Журнал: Organometallics
Том: 41
Год издания: 2022
Издательство: American Chemical Society
Местоположение издательства: United States
Первая страница: 1631
Последняя страница: 1639
DOI: 10.1021/acs.organomet.2c00130
Аннотация: The interaction of seven-membered zirconacyclocumulene 1 and zirconacyclopentadiene 9 complexes of zirconocene with a two-fold excess of acetonitrile results in the formation of vinyl-acetamidine zirconabicycles 7 and 11. Both reactions proceed via the intermediate generation of the acetylene complexes of zirconocene and the subsequent vinyl-acetamidination of these complexes with the formation of final complexes 7 and 11. The reaction of dimeric zirconaazacyclopentadiene metallacycle 2 with one equivalent of acetonitrile at 100°C in toluene also results in the formation of complex 7. The obtained complex 7 is capable of undergoing unusual thermal isomerization with the formation of strained triheterocyclic complex 8 containing a T-shaped pyrrole carbon atom. This isomerisation proceeds even in absence of any solvents with almost quantitative yield at 140°C for 45 h. The structures of 7, 8 and 11 have been determined by X-ray diffraction.
Добавил в систему: Тугашов Кирилл Игоревич

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