Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 27th March 2019 from 11:00 AM to 1:00 PM (GMT).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 43, 2018
Previous Article Next Article

Non-innocent PNN ligand is important for CO oxidation by N2O catalyzed by a (PNN)Ru–H pincer complex: insights from DFT calculations

Author affiliations

Abstract

Milstein et al. developed an efficient and mild method for CO oxidation by N2O to give CO2 and N2 catalyzed by a (PNN)Ru–H pincer complex. To gain mechanistic information on this catalytic transformation, the reaction mechanism has been studied using density functional theory (DFT) calculations. It was found that the catalytic cycle for CO oxidation by N2O proceeds in three stages: N2O activation to form a (PNN)Ru–OH intermediate, CO insertion into the Ru–OH bond to form a (PNN)Ru–COOH intermediate and CO2 release from (PNN)Ru–COOH. In the CO2 release stage, CO2 is not released via a β-H elimination mechanism as proposed in experiments, instead it is released via a deprotonation mechanism. The calculations demonstrated that the Ru–H bond of the catalyst plays an important role in facilitating the activation of N2O, which is the rate-determining step for the whole catalytic cycle, and the non-innocent PNN ligand is very important for CO oxidation by N2O. Our theoretical results are consistent with the experimental observations and could help design highly efficient catalysts for N2O activation.

Graphical abstract: Non-innocent PNN ligand is important for CO oxidation by N2O catalyzed by a (PNN)Ru–H pincer complex: insights from DFT calculations

Back to tab navigation

Supplementary files

Publication details

The article was received on 13 Aug 2018, accepted on 27 Sep 2018 and first published on 28 Sep 2018


Article type: Paper
DOI: 10.1039/C8DT03304H
Citation: Dalton Trans., 2018,47, 15324-15330

  •   Request permissions

    Non-innocent PNN ligand is important for CO oxidation by N2O catalyzed by a (PNN)Ru–H pincer complex: insights from DFT calculations

    H. Xie, Y. Zhang, C. Xiang, Y. Li, T. Fan, Q. Lei and W. Fang, Dalton Trans., 2018, 47, 15324
    DOI: 10.1039/C8DT03304H

Search articles by author

Spotlight

Advertisements