Influence of the N→Ru Coordinate Bond Length on the Activity of New Types of Hoveyda-Grubbs Olefin Metathesis Catalysts Containing a Six-Membered Chelate Ring Possessing a Ruthenium-Nitrogen Bond

An efficient approach to the synthesis of new types of Hoveyda-Grubbs catalysts containing an N→Ru bond in a six-membered chelate ring is proposed. The synthesis of the organometallic compounds is based on the interaction of ready accessible 2-vinylbenzylamines and 1,3-bis(2,4,6-trimethylphenyl)-2-trichloromethylimidazolidine ligands with dichloro(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphane)ruthenate, and it afforded the target ruthenium complexes in 70-80% yields. Areas of practical utility and potential applications of the obtained chelates were highlighted by tests of the catalysts in different olefin cross-metathesis (CM) and ring-closing-metathesis (RCM) reactions. These experiments revealed a high catalytic performance (up to 10-2 mol %) of all the synthesized structures in a broad temperature range. The structural peculiarities of the resultant ruthenium catalysts were thoroughly investigated by X-ray crystallography, which allowed making a reliable correlation between the structure of the metallo-complexes and their catalytic properties. It was proved that the bond length between ruthenium and nitrogen in the six-membered chelate ring has the greatest effect on the stability and efficiency of the catalyst. As a rule, the shorter and stronger the N→Ru bond, the higher the stability of the complex and the worse its catalytic characteristics. In turn, the coordination N→Ru bond length can be finely tuned and varied over a wide range of values by changing the steric volume of the cyclic substituents at the nitrogen atom, which will make it possible, as appropriate, to obtain in the future metal complexes with predictable stability and the required catalytic activity. Also, it was found that complexes in which the nitrogen atom is included in the morpholine or isoquinoline rings are the most efficient catalysts in this series. An attempt to establish a correlation between the N→Ru bond length and the 1H and 13C chemical shifts in the RuCH fragment has been made. © 2020 American Chemical Society.

Kumandin P.A. 1 , Antonova A.S. 1 , Alekseeva K.A. 1 , Nikitina E.V. 1 , Novikov R.A. 2 , Vasilyev K.A. 1 , Sinelshchikova A.A.3 , Grigoriev M.S.3 , Polyanskii K.B. 1 , Zubkov F.I. 1
American Chemical Society
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  • 1 Organic Chemistry Department, Faculty of Science, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St., Moscow, 117198, Russian Federation
  • 2 N. D. Zelinsky Institute of Organic Chemistry of Ras, 47 Leninsky Prospect, Moscow, 119991, Russian Federation
  • 3 Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 31 Leninsky Prospect, bld. 4, Moscow, 119071, Russian Federation
Ключевые слова
Catalyst activity; Chelation; Coordination reactions; Metal complexes; Nitrogen; Olefins; Organometallics; Ruthenium compounds; Synthesis (chemical); X ray crystallography; 1H and 13C chemical shifts; Broad temperature ranges; High catalytic performance; Hoveyda-grubbs catalyst; Olefin cross-metathesis; Organometallic compounds; Ring-closing metathesis reactions; Structural peculiarities; Bond length
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