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

摘要

The synthesis and reaction of homoleptic iron(II) complexes with 2,6-di-adamantyl-substituted aryloxides [OC_6H_2-2,6-Ad-4-R] - ([OAr~(AdR)]~-, Ad = adamantyl, R = Me, ~iPr) are described. Monomeric two-coordinate iron aryloxides Fe(OAr~(AdR))_2 (R = Me, 1; ~iPr, 2) were synthesized by the reaction of Fe[N(SiMe_3)_2]_2 with 2 equiv of HOAr~(AdR). 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(OAr~(AdR))(OAr~(AdR)-NHAd) (R = Me, 3; ~iPr, 4). Molecular structures of all these complexes are reported.