Oxoiron(IV) species are key intermediates in the catalytic cycles of numerous heme and non-heme iron enzymes that insert an O atom from dioxygen into unactivated C�H bonds.1 Because of the enormous importance of such oxygenase reactions in biology as well as in synthetic chemistry, over the last decade much effort has been devoted to the isolation and characterization of those reactive oxoiron(IV) intermediates and to the understanding of their reactivity patterns. So far bioinspired oxoiron(IV) model complexes are exclusively stabilized by multidentate N-donor ligands,2 though N-heterocyclic carbene ligands have proven particularly useful for stabilizing and isolating high-valent iron nitrido species.3 We report that a macrocyclic tetracarbene framework, recently developed by Cramer and Jenkins,4 efficiently stabilizes the oxoiron(IV) unit. This made possible the first isolation and structural characterization of an organometallic oxoiron(IV) complex which has an electronic structure and spectroscopic signatures distinct from those of other oxoiron(IV) complexes.5References1.J. Hohenberger, K. Ray, K. Meyer, Nat. Commun. 2012  , 3, 720-732.2. A. R. McDonald, L. Que Jr., Coord. Chem. Rev. 2013  , 257, 414� 428.3. J. J. Scepaniak, C. S. Vogel, M. M. Khusniyarov, F. W. Heinemann, K. Meyer, J. M. Smith, Science 2011  , 331, 1049-1052.4. H. M. Bass, S. A. Cramer, J. L. Price, D. M. Jenkins, Organometallics 2010  , 29, 3235-3238.5. S. Meyer, I. Klawitter, S. Demeshko, E. Bill, F. Meyer, Angew. Chem. Int. Ed. 2013  , 52, 901 �905.

Bioinorganic meets organometallic: A tetracarbene-oxoiron(IV) complex

247th National Meeting (2014)

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