Alcohol Amination with Ammonia Catalyzed by an Acridine-Based Ruthenium Pincer Complex: A Mechanistic Study

Abstract

The mechanistic course of the amination of alcohols with ammonia catalyzed by a structurally modified congener of Milstein's well-defined acridine-based PNP-pincer Ru complex has been investigated both experimentally and by DFT calculations. Several key Ru intermediates have been isolated and characterized. The detailed analysis of a series of possible catalytic pathways (e.g., with and without metal-ligand cooperation, inner- and outer-sphere mechanisms) leads us to conclude that the most favorable pathway for this catalyst does not require metal-ligand cooperation.

Computational Mechanistic Studies on Reactions of Transition Metal Complexes with Noninnocent Pincer Ligands: Aromatization–Dearomatization or Not

“…[49][50][51][52][53][54][55][56] In addition, a theoretical study about the ruthenium acridine complex was also reported. 57 These theoretical studies are discussed in the following sections.…”

“…1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 21 Scheme 44: Proposed mechanism for the initial dearomatization of 189 to give 192 by Hofmann and coworkers. 57 Scheme 45: Proposed mechanism for the amination of alcohol with NH3 by Hofmann and coworkers. 57…”

Metall‐Ligand‐Kooperation

“…Vor kurzem synthetisierten Hofmann et al. einen analogen Komplex 172 mit PCy 2 ‐substituiertem AcrPNP Cy ‐Liganden, der ebenfalls katalytische Aktivität in der Aminierung von Alkoholen mit Ammoniak zeigte 137. Die stöchiometrische Reaktion von 172 mit einem Alkohol in der Gegenwart einer Base führt zur Reduktion des zentralen Acridinrings und Bildung von 173 (Schema ).…”

“…Die stöchiometrische Reaktion von 172 mit einem Alkohol in der Gegenwart einer Base führt zur Reduktion des zentralen Acridinrings und Bildung von 173 (Schema ). Eine DFT‐Analyse der Reaktion mit MeOH als Modellsubstrat zeigte, dass ein plausibler Mechanismus mit der Bildung eines Alkoxid‐Komplexes beginnt, gefolgt vom Hydridtransfer von der CH 2 ‐Gruppe des Alkohols zum C9‐Kohlenstoff des zentralen Acridinrings (Schemaa ) 137…”

Formation and nitrile hydrogenation performance of Ru nanoparticles on a K-doped Al2O3 surface

“…[1][2][3][4][5][6][7][8] Selectivity for primary amines is a crucial problem in the preparation of amines because of the facile formation of secondary and tertiary amines under the reaction conditions. Reductive amination of aldehydes and ketones and hydrogenation of nitriles are wellknown amine preparation methods.…”