Issue 44, 2019

Selectivity of tungsten mediated dinitrogen splitting vs. proton reduction

Abstract

Mo complexes are currently the most active catalysts for nitrogen fixation under ambient conditions. In comparison, tungsten platforms are scarcely examined. For active catalysts, the control of N2vs. proton reduction selectivities remains a difficult task. We here present N2 splitting using a tungsten pincer platform, which has been proposed as the key reaction for catalytic nitrogen fixation. Starting from [WCl3(PNP)] (PNP = N(CH2CH2PtBu2)2), the activation of N2 enabled the isolation of the dinitrogen bridged redox series [(N2){WCl(PNP)}2]0/+/2+. Protonation of the neutral complex results either in the formation of a nitride [W(N)Cl(HPNP)]+ or H2 evolution and oxidation of the W2N2 core, respectively, depending on the acid and reaction conditions. Examination of the nitrogen splitting vs. proton reduction selectivity emphasizes the role of hydrogen bonding of the conjugate base with the protonated intermediates and provides guidelines for nitrogen fixation.

Graphical abstract: Selectivity of tungsten mediated dinitrogen splitting vs. proton reduction

Supplementary files

Article information

Article type
Edge Article
Submitted
30 Jul 2019
Accepted
19 Sep 2019
First published
24 Sep 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 10275-10282

Selectivity of tungsten mediated dinitrogen splitting vs. proton reduction

B. Schluschaß, J. Abbenseth, S. Demeshko, M. Finger, A. Franke, C. Herwig, C. Würtele, I. Ivanovic-Burmazovic, C. Limberg, J. Telser and S. Schneider, Chem. Sci., 2019, 10, 10275 DOI: 10.1039/C9SC03779A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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