Influence of Substituents in a Six-Membered Chelate Ring of HG-Type Complexes Containing an N→Ru Bond on Their Stability and Catalytic Activity
Kirill A. Vasilyev,
Alexandra S. Antonova,
Nikita S. Volchkov,
Nikita A. Logvinenko,
Eugeniya V. Nikitina,
Mikhail S. Grigoriev,
Anton P. Novikov,
Vladimir V. Kouznetsov,
Kirill B. Polyanskii,
Fedor I. Zubkov
Affiliations
Kirill A. Vasilyev
Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), Miklukho-Maklaya St., 6, Moscow 117198, Russia
Alexandra S. Antonova
Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), Miklukho-Maklaya St., 6, Moscow 117198, Russia
Nikita S. Volchkov
Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), Miklukho-Maklaya St., 6, Moscow 117198, Russia
Nikita A. Logvinenko
Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), Miklukho-Maklaya St., 6, Moscow 117198, Russia
Eugeniya V. Nikitina
Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), Miklukho-Maklaya St., 6, Moscow 117198, Russia
Mikhail S. Grigoriev
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky pr. 31, bld. 4, Moscow 119071, Russia
Anton P. Novikov
Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), Miklukho-Maklaya St., 6, Moscow 117198, Russia
Vladimir V. Kouznetsov
Laboratorio de Química Orgánica y Biomolecular, Escuela de Química, Universidad Industrial de Santander, Cl. 9 # Cra 27, Bucaramanga 680006, Colombia
Kirill B. Polyanskii
Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), Miklukho-Maklaya St., 6, Moscow 117198, Russia
Fedor I. Zubkov
Organic Chemistry Department, Faculty of Science, Peoples’ Friendship University of Russia (RUDN University), Miklukho-Maklaya St., 6, Moscow 117198, Russia
An efficient approach to the synthesis of olefin metathesis HG-type catalysts containing an N→Ru bond in a six-membered chelate ring was proposed. For the most part, these ruthenium chelates can be prepared easily and in high yields based on the interaction between 2-vinylbenzylamines and Ind II (the common precursor for Ru-complex synthesis). It was demonstrated that the increase of the steric volume of substituents attached to the nitrogen atom and in the α-position of the benzylidene fragment leads to a dramatic decrease in the stability of the target ruthenium complexes. The bulkiest iPr substituent bonded to the nitrogen atom or to the α-position does not allow the closing of the chelate cycle. N,N-Diethyl-1-(2-vinylphenyl)propan-1-amine is a limiting case; its interaction with Ind II makes it possible to isolate the corresponding ruthenium chelate in a low yield (5%). Catalytic activity of the synthesized complexes was tested in RCM reactions and compared with α-unsubstituted catalysts obtained previously. The structural peculiarities of the final ruthenium complexes were thoroughly investigated using XRD and NMR analysis, which allowed making a reliable correlation between the structure of the complexes and their catalytic properties.
