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Protonation and electrochemical reduction of rhodium– and iridium–dinitrogen complexes in organic solution

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Abstract

Protonation and reduction of pincer-ligated Rh– and Ir–N2 complexes have been studied by NMR spectroscopy and cyclic voltammetry to assess the capability of these complexes to activate or reduce N2. Protonation, which is a prerequisite to electrochemical reduction, results in a cationic metal-hydride that loses N2 under an atmosphere of Ar. Reduction of the metal-hydride results in fast disproportionation of an unobserved transient Ir2+ species. These studies suggest that the regioselectivity of initial protonation is a strong determinant for the ability of a system to facilitate the reduction of N2.

Graphical abstract: Protonation and electrochemical reduction of rhodium– and iridium–dinitrogen complexes in organic solution

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Publication details

The article was received on 15 Sep 2017, accepted on 02 Oct 2017 and first published on 11 Oct 2017


Article type: Paper
DOI: 10.1039/C7DT03476H
Citation: Dalton Trans., 2017, Advance Article
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    Protonation and electrochemical reduction of rhodium– and iridium–dinitrogen complexes in organic solution

    G. P. Connor, N. Lease, A. Casuras, A. S. Goldman, P. L. Holland and J. M. Mayer, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT03476H

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