Coupling of terminal iridium nitrido complexes

J. Abbenseth; Markus Finger; Christian Würtele; Müge Kasanmascheff; Sven Schneider

doi:10.1039/c5qi00267b

Coupling of terminal iridium nitrido complexes

J. Abbenseth, Markus Finger, Christian Würtele, Müge Kasanmascheff, Sven Schneider^*

^*Corresponding author for this work

Inorganic Chemistry Group

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	469-477
Number of pages	9
Journal	Inorganic Chemistry Frontiers
Volume	3
Issue number	4
Early online date	15 Jan 2016
DOIs	https://doi.org/10.1039/c5qi00267b
Publication status	Published - 1 Apr 2016

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title = "Coupling of terminal iridium nitrido complexes",

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.",

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T1 - Coupling of terminal iridium nitrido complexes

AU - Abbenseth, J.

AU - Finger, Markus

AU - Würtele, Christian

AU - Kasanmascheff, Müge

AU - Schneider, Sven

PY - 2016/4/1

Y1 - 2016/4/1

N2 - 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.

AB - 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.

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JO - Inorganic Chemistry Frontiers

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Coupling of terminal iridium nitrido complexes

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