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Issue 4, 2016
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Coupling of terminal iridium nitrido complexes

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Abstract

The oxidative coupling of nitride ligands (N3−) to dinitrogen and its microscopic reverse, N2-splitting to nitrides, are important elementary steps in chemical transformations, such as selective ammonia oxidation or nitrogen fixation. Here an experimental and computational evaluation is provided for the homo- and heterocoupling of our previously reported iridium(IV) and iridium(V) nitrides [IrN(PNP)]n (n = 0, +1; PNP = N(CHCHPtBu2)2). All three formal coupling products [(PNP)IrN2Ir(PNP)]n (n = 0–+2) were structurally characterized. While the three coupling reactions are all thermodynamically feasible, homocoupling of [IrN(PNP)]+ is kinetically hindered. The contributing parameters to relative coupling rates are discussed providing qualitative guidelines for the stability of electron rich transition metal nitrides.

Graphical abstract: Coupling of terminal iridium nitrido complexes

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Supplementary files

Article information


Submitted
28 Nov 2015
Accepted
12 Jan 2016
First published
15 Jan 2016

This article is Open Access

Inorg. Chem. Front., 2016,3, 469-477
Article type
Research Article
Author version available

Coupling of terminal iridium nitrido complexes

J. Abbenseth, M. Finger, C. Würtele, M. Kasanmascheff and S. Schneider, Inorg. Chem. Front., 2016, 3, 469
DOI: 10.1039/C5QI00267B

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