Jump to main content
Jump to site search

Issue 5, 2020

Mechanistic diversity in acetophenone transfer hydrogenation catalyzed by ruthenium iminophosphonamide complexes

Author affiliations

Abstract

A series of arene ruthenium iminophosphonamide complexes, [(Arene)RuCl{R2P(NR′)2}] (1), bearing various arenes and R,R′ substituents on the NPN ligand have been investigated as precatalysts in acetophenone transfer hydrogenation in basic and base-free isopropanol. The results clearly demonstrate the presence of two distinct reaction mechanisms, which are controlled by the basicity of the N-atoms. Complexes 1 in which both R′ substituents are aryl groups are only active once the neutral hydride complex [(Arene)RuH{R2P(NR′)2}] (2) is generated in basic isopropanol, the latter being able to reduce a ketone via a stepwise hydride and proton transfer. On the other hand, complexes in which at least one R′ group is Me readily catalyze the reaction in the absence of base. In the latter case, the results of kinetic studies and DFT calculations support an outer-sphere concerted asynchronous hydride and proton transfer assisted by the basic N-atom of the NPN ligand, which promotes catalysis via precoordination of an alcohol molecule by hydrogen bonding.

Graphical abstract: Mechanistic diversity in acetophenone transfer hydrogenation catalyzed by ruthenium iminophosphonamide complexes

Supplementary files

Article information


Submitted
25 Nov 2019
Accepted
23 Dec 2019
First published
26 Dec 2019

Dalton Trans., 2020,49, 1473-1484
Article type
Paper

Mechanistic diversity in acetophenone transfer hydrogenation catalyzed by ruthenium iminophosphonamide complexes

A. M. Kalsin, T. A. Peganova, I. S. Sinopalnikova, I. V. Fedyanin, N. V. Belkova, E. Deydier and R. Poli, Dalton Trans., 2020, 49, 1473 DOI: 10.1039/C9DT04532E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.


Social activity

Search articles by author

Spotlight

Advertisements