Terminal nitrido complexes with high metal dn valence electron counts (n = 4) are of high interest as models for nitrogen fixation.[1] However, examples are exceedingly rare. In this contribution we present square-planar 15 and 14 VE complexes (1  and 2  ), stabilized by a PNP pincer ligand.[2] These compounds are excellent platforms for the synthesis of closed-shell and open-shell iridium nitrido complexes (4  and 5  ). Their electronic structures will be discussed and the reactivity towards N/O and N/N coupling will be presented.[3] The unpaired electron in 5  is strongly delocalized within the Ir-N moiety, hence, representing a unique example of a complex with predominant nitridyl character. [1] B. Askevold, J. T. Nieto, S. Tussupbayev, M. Diefenbach, E. Herdtweck, M. C. Holthausen, S. Schneider, Nature Chem., 2011  , 3, 532.[2] J. Meiners, M. G. Scheibel, M.-H. Lem�e-Cailleau, S. A. Mason, M. B. Boeddinghaus, T. F. F�ssler, E. Herdtweck, M. M. Khusniyarov, S. Schneider, Angew. Chem. Int. Ed., 2011  , 50, 8184.[3] M. G. Scheibel, B. Askevold, F. Heinemann, B. de Bruin, S. Schneider, submitted.

Square-planar iridium(I-V) PNP pincer complexes: Closed and open shell iridium nitrides

243rd National Meeting (2012)

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