Synthesis of two-coordinate iron aryloxides and their reactions with organic azide: Intramolecular C-H bond amination

The synthesis and reaction of homoleptic iron(II) complexes with 2,6-di-adamantyl-substituted aryl-oxides [OC6H2-,6-Ad-4-R](-) ([OArAdR](-), Ad = adamantyl, R = Me, Pr-i) are described. Monomeric two-coordinate iron aryloxides Fe(OArAdR)(2)(R = Me, 1; Pr-i, 2) were synthesized by the reaction of Fe [N(SiMe3)(2)](2) with 2 equiv of HOArAdR. Treatment of 1 and 2 with 1-azidoadamantane resulted in intramolecular insertion of an adamantyl nitrene into a methylene C-H bond of the aryloxide adamantyl substituent, yielding the corresponding amine-aryloxide complexes Fe(OArAdR)(OArAdR-NHAd) (R = Me, 3; Pr-i, 4). Molecular structures of all these complexes are reported. (C) 2011 Elsevier B.V. All rights reserved.