Indenyl Rhodium Complexes with Arene Ligands: Synthesis and Application for Reductive Amination

An efficient protocol for synthesis of indenyl rhodium complexes with arene ligands has been developed. The hexafluoroantimonate salts [(σ5-indenyl)Rh(arene)](SbF6)2 (arene = benzene (2a), o-xylene (2b), mesitylene (2c), durene (2d), hexamethylbenzene (2e), and [2.2]paracyclophane (2g)) were obtained by iodide abstraction from [(σ5-indenyl)RhI2]n (1) with AgSbF6 in the presence of benzene and its derivatives. The procedure is also suitable for the synthesis of the dirhodium arene complex [(μ-σ:σ′-1,3-dimesitylpropane){Rh(σ5-indenyl)}2](SbF6)4 (3) starting from 1,3-dimesitylpropane. The structures of [2e](SbF6)2, [2g](SbF6)2, and [3](SbF6)4 were determined by X-ray diffraction. The last species has a sterically unfavorable conformation, in which the bridgehead carbon atoms of the indenyl ligand are arranged close to the propane linker between two mesitylene moieties. Experimental and DFT calculation data revealed that the benzene ligand in 2a is more labile than that in the related cyclopentadienyl complexes [(C5R5)Rh(C6H6)]2+. Complex 2c effectively catalyzes the reductive amination reaction between aldehydes and primary (or secondary) amines in the presence of carbon monoxide, giving the corresponding secondary and tertiary amines in very high yields (80-99%). This protocol is the most active in water. © 2018 American Chemical Society.

Авторы
Kharitonov V.B.1 , Makarova M. 2 , Arsenov M.A.1 , Nelyubina Y.V.1 , Chusova O. 3 , Peregudov A.S.1 , Zlotskii S.S.4 , Chusov D. 1 , Loginov D.A.1
Журнал
Издательство
American Chemical Society
Номер выпуска
15
Язык
Английский
Страницы
2553-2562
Статус
Опубликовано
Том
37
Год
2018
Организации
  • 1 A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova str. 28, Moscow, 119991, Russian Federation
  • 2 Dmitry Mendeleev University of Chemical Technology of Russia, Miusskaya sq. 9, Moscow, 125047, Russian Federation
  • 3 Faculty of Science, RUDN University, 6 Miklukho-Maklaya St., Moscow, 117198, Russian Federation
  • 4 Ufa Oil Institute, Kosmonavtov Str., 1, Ufa, 450062, Russian Federation
Дата создания
19.10.2018
Дата изменения
19.10.2018
Постоянная ссылка
https://repository.rudn.ru/ru/records/article/record/6460/