Iron Coordination and Halogen-Bonding Assisted Iodosylbenzene Activation

Christina Wegeberg, David Poulsen de Sousa, Christine McKenzie

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The iron complex of the hexadentate ligand N,N,N'-tris(2-pyridylmethyl)ethylendiamine-N'-acetate (tpena) efficiently catalyzes selective oxidations of electron-rich olefins and sulfides by insoluble iodosylbenzene (PhIO). Surprisingly, these reactions are faster and more selective than homogenous catalytic mixtures using soluble terminal oxygen transfer agents. Isolation of a reactive iron-terminal oxidant adduct, an unique Fe(III)-OIPh complex, is facilitated by strong stabilizing supramolecular halogen-bonding. L3-edge XANES suggests +1.6 for the average oxidation state for the iodine atom3 in the iron(III)-coordinated PhIO. This represents a reduction of iodine relative to the original “hypervalent” (+3) PhIO. The equivalent of electron density must be removed from the {(tpena)Fe(III)O} moiety, however Mössbauer spectroscopy shows that the iron atom is not high valent.
Original languageEnglish
Publication date2016
Number of pages1
Publication statusPublished - 2016
Event42nd International Conference of Coordination Chemistry - Brest, France
Duration: 3. Jul 20168. Jul 2016
Conference number: 42


Conference42nd International Conference of Coordination Chemistry
Internet address

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