We have previously reported the unique cis-divacant octahedral coordination geometry of a tertbutyl-substituted pyridine bis-pyrrolide (pyrpyrr2) ligand with iron complexes in three oxidation states.[1] This coordination geometry also applies to doubly and quadruply reduced dimeric dinitrogen complexes which show significant activation of the N-N bond (1.189 Å and 1.222 Å for the N-N bond in the doubly and quadruply reduced complexes, respectively). The dinitrogen unit bridges the two iron atoms with a Fe-Fe-N(N2) angle of 17.26° and 21.79° for the doubly and quadruply reduced dinitrogen complexes, respectively. Cis-divacant octahedral geometry is also observed following reaction of a Fe(II) pyrpyrr2 diethyl ether adduct with benzyl azide which forms an Fe(II) pyrpyrr2 benzaldimine adduct. An additional equivalent of benzyl azide forms a mono-vacant octahedral bis benzaldimine adduct with a vacant coordination site trans to the pyridine N-atom, foregoing tetrazadiene formation observed in similar systems. In this study I will discuss the reactivity and coordination chemistry of Fe complexes supported by this tridentate ligand with dinitrogen and organic azide reagents.

Redox-noninnocent pyridine bispyrrolide ligand enables unique coordination modes in iron complexes with dinitrogen and benzyl azide

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.