21040-45-9Relevant articles and documents
Ouellette et al.
, p. 2744 (1964)
Ouellette,R.J.,Shaw,D.L.
, p. 1651 - 1652 (1964)
An air-tolerant polymer gel-immobilized iridium photocatalyst with pumping recyclability properties
Abramov, Alex,Díaz Díaz, David,Maiti, Binoy,Reiser, Oliver
supporting information, p. 7762 - 7765 (2021/08/13)
A novel methacrylate-based cross-linked polymer gel bearing an iridium photocatalyst showed air tolerance and pumping recyclability features through its tunable swelling and deswelling ability. The photocatalytic activity of the polymer gel was demonstrated through an E-to-Z isomerisation reaction and in an azide-alkene [2+3] cycloaddition.
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
Alekseeva, Kseniia A.,Antonova, Alexandra S.,Grigoriev, Mikhail S.,Kumandin, Pavel A.,Nikitina, Eugeniya V.,Novikov, Roman A.,Polyanskii, Kirill B.,Sinelshchikova, Anna A.,Vasilyev, Kirill A.,Zubkov, Fedor I.
supporting information, p. 4599 - 4607 (2020/12/22)
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 Ru═CH fragment has been made.
