Closed-shell and open-shell square-planar iridium nitrido complexes

Scheibel MG, Askevold B, Heinemann FW, Reijerse EJ, De Bruin B, Schneider S (2012)

Publication Status: Published

Publication Type: Journal article

Publication year: 2012

Journal

Nature Chemistry Nature Publishing Group

Publisher: NATURE PUBLISHING GROUP

Book Volume: 4

Pages Range: 552-558

Journal Issue: 7

DOI: 10.1038/NCHEM.1368

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)].

Authors with CRIS profile

Frank Wilhelm Heinemann Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Max-Planck-Institut für Chemische Energiekonversion (MPI CEC) / Max-Planck-Institute for Chemical Energy Conversion DE Germany (DE) Georg-August-Universität Göttingen DE Germany (DE) University of Amsterdam NL Netherlands (NL)

How to cite

APA:

Scheibel, M.G., Askevold, B., Heinemann, F.W., Reijerse, E.J., De Bruin, B., & Schneider, S. (2012). Closed-shell and open-shell square-planar iridium nitrido complexes. Nature Chemistry, 4(7), 552-558. https://doi.org/10.1038/NCHEM.1368

MLA:

Scheibel, Markus G., et al. "Closed-shell and open-shell square-planar iridium nitrido complexes." Nature Chemistry 4.7 (2012): 552-558.

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