Closed-shell and open-shell square-planar iridium nitrido complexes
2012 | journal article. A publication with affiliation to the University of Göttingen.
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- Authors
- Scheibel, Markus G.; Askevold, Bjorn; Heinemann, Frank W.; Reijerse, Edward J.; de Bruin, Bas; Schneider, Sven
- Abstract
- Coupling reactions of nitrogen atoms represent elementary steps to many important heterogeneously catalysed reactions, such as the Haber-Bosch process or the selective catalytic reduction of NOx to give N-2. For molecular nitrido (and related oxo) complexes, it is well established that the intrinsic reactivity, for example nucleophilicity or electrophilicity of the nitrido (or oxo) ligand, can be attributed to M-N (M-O) ground-state bonding. In recent years, nitrogen (oxygen)-centred radical reactivity was ascribed to the possible redox non-innocence of nitrido (oxo) ligands. However, unequivocal spectroscopic characterization of such transient nitridyl {M=N-center dot} (or oxyl {M-O-center dot}) complexes remained elusive. Here we describe the synthesis and characterization of the novel, closed-shell and open-shell square-planar iridium nitrido complexes [IrN(Lt-Bu)](+) and [IrN(Lt-Bu)] (Lt-Bu=N(CHCHP-t-Bu-2)(2)). Spectroscopic characterization and quantum chemical calculations for [IrN(Lt-Bu)] indicate a considerable nitridyl, {Ir=N-center dot}, radical character. The clean formation of Ir-I-N-2 complexes via binuclear coupling is rationalized in terms of nitrido redox non-innocence in [IrN(Lt-Bu)].
- Issue Date
- 2012
- Status
- published
- Publisher
- Nature Publishing Group
- Journal
- Nature Chemistry
- ISSN
- 1755-4349; 1755-4330