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Rare-earth metal mediated PhCN insertion into N,N-bis(trimethylsilyl)naphthalene-1,8-diamido dianion – a synthetic approach to complexes coordinated by ansa-bridged amido-amidinato ligand. Synthesis, structures and catalytic activityстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
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Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 23 января 2018 г.
- Авторы: Lyubov Dmitry M., Cherkasov Anton V., Fukin Georgy K., Lyssenko Konstantin A., Rychagova Elena A., Ketkov Sergey Yu, Trifonov Alexander A.
- Журнал: Dalton Transactions
- Том: 47
- Номер: 2
- Год издания: 2018
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 438
- Последняя страница: 451
- DOI: 10.1039/c7dt03809g
- Аннотация: Lithium silylamides 1,8-C10H6[N(SiMe3)Li(L)](2) (L = Et2O (1(Et2O)); L = TMEDA (1(TMEDA))), when treated with PhC N, formed the adducts 1,8-C10H6[N(SiMe3)Li(N CPh)(OEt2)][N(SiMe3) Li(OEt2)] (2(Et2O)) and 1,8-C10H6[N(SiMe3)Li(N CPh)][N(SiMe3)Li(TMEDA)] (2(TMEDA)) containing one benzonitrile molecule coordinated to Li ion while the second molecule retains a coordinated L ligand. The salt metathesis reactions of LnCl(3) (Ln = Y, Sm) with equimolar amounts of 2(Et2O) and 2(TMEDA) (THF, 4 h, 40 degrees C) resulted in benzonitrile insertion and formation of new dianionic amido-amidinate ligands. The reactions of 2(Et2O) with LnCl(3) afforded ionic chloro complexes [{1,8-C10H6[NSiMe3][NC(Ph) NSiMe3]}{1,8-C10H6[N(H) SiMe3][NC(Ph) NSiMe3]} LnCl][Li(L)(n)] (Ln = Y, L = THF, n = 4 (3Y), Ln = Sm, L = DME, n = 3 (3Sm)), while the reaction of 2(TMEDA) and YCl3 leds to the formation of the neutral salt-free yttrium chloro complex {1,8-C10H6[NSiMe3][NC(Ph) NSiMe3]}YCl(TMEDA) (4). The treatment of 3Y and 4 with tBuOK enabled the synthesis of tert-butoxides [{1,8-C10H6[NSiMe3][NC(Ph)NSiMe3]}{1,8-C10H6[N(H)SiMe3][NC(Ph)NSiMe3]} YOtBu][Li(THF)(4)] (7) and {1,8-C10H6[NSiMe3][NC(Ph)NSiMe3]}YOtBu(TMEDA) (8). Complexes 7 and 8 were evaluated as initiators for the ring opening polymerization of rac-lactide. Neutral tert-butoxide complex 8 demonstrated significantly higher activity compared to that of ionic 7.
- Добавил в систему: Лысенко Константин Александрович