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Journal Article

Coupling of terminal iridium nitrido complexes.

MPS-Authors
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Kasanmascheff,  M.
Research Group of Electron Paramagnetic Resonance, MPI for Biophysical Chemistry, Max Planck Society;

External Ressource
Fulltext (public)

2254917.pdf
(Publisher version), 2MB

Supplementary Material (public)

2254917_Suppl_1.pdf
(Supplementary material), 9MB

2254917_Suppl_2.cif
(Supplementary material), 4MB

Citation

Abbenseth, J., Finger, M., Würtele, C., Kasanmascheff, M., & Schneider, S. (2016). Coupling of terminal iridium nitrido complexes. Inorganic Chemistry Frontiers, 3(4), 469-477. doi:10.1039/C5QI00267B.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0029-CD5F-C
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.