Author: ["Markus G. Scheibel","Bjorn Askevold","Frank W. Heinemann","Edward J. Reijerse","Bas de Bruin","Sven Schneider"]
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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 N2. 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•} (or oxyl {M–O•}) 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-Bu2)2). Spectroscopic characterization and quantum chemical calculations for [IrN(Lt-Bu)] indicate a considerable nitridyl, {Ir=N•}, radical character. The clean formation of IrI–N2 complexes via binuclear coupling is rationalized in terms of nitrido redox non-innocence in [IrN(Lt-Bu)]. Coupling reactions of nitrogen atoms represent elementary steps to many important, heterogeneously catalysed reactions, such as the Haber–Bosch process or selective catalytic reduction of NOx to N2. Here, the synthesis and characterization of closed- and open-shell, square-planar iridium nitrido complexes is described, indicating considerable nitridyl radical character for the open shell complex. Cite this article
Scheibel, M., Askevold, B., Heinemann, F. et al. Closed-shell and open-shell square-planar iridium nitrido complexes. Nature Chem 4, 552–558 (2012). https://doi.org/10.1038/nchem.1368 