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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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Publication details

The article was received on 28 Nov 2015, accepted on 12 Jan 2016 and first published on 15 Jan 2016


Article type: Research Article
DOI: 10.1039/C5QI00267B
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Citation: Inorg. Chem. Front., 2016,3, 469-477
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    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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