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Reversible C-C Bond Formation in Group 4 Metal Complexes: Nitrile Extrusion via β-Aryl Eliminationстатья
Статья опубликована в высокорейтинговом журнале
Статья опубликована в журнале из списка Web of Science и/или Scopus- Авторы: Kulyabin Pavel, Goryunov Georgy, Iashin Andrei, Mladentsev Dmitry, Uborsky Dmitry, Ehm Christian, Hagadorn John R., Canich Joann, Voskoboynikov Alexander
- Журнал: Chemical science
- Том: 15
- Год издания: 2024
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 15825
- Последняя страница: 15834
- DOI: 10.1039/D4SC02173H
- Аннотация: Pyridylamides of zirconium and hafnium with [C,N,N]-ligands reversibly insert nitriles into M–CAr bond forming an equilibria between the starting [C,N,N]-complexes and newly formed [N,N,N]-complexes with ketimide moiety in a 7-membered metallacycle. The discovered reversible insertion of nitriles into M–CAr bonds represents an unprecedented example of β-aryl elimination from a ketimide ligand in early transition metals complexes. Experimental and computational studies suggest thermodynamic and electronic reasoning for this reactivity. Weak orbital overlap between the ketimide nitrogen and the metal, and unfavorable 7-membered metallacycle destabilize the product of insertion into the M–CAr bond, while the pyridylamide moiety acts as a directing group making the reverse process viable. Influence of non-chelate spectator ligands on the metal center and substituents in the nitrile on the thermodynamic stability of the [N,N,N]-complexes were also studied. Exploiting β-carbon elimination in complexes of early transition metals may extend the range of catalysts that are accessible for C–C activation processes in the future.
- Добавил в систему: Уборский Дмитрий Вадимович
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