ic302634q_si_001.pdf (2.4 MB)
Iron in a Trigonal Tris(alkoxide) Ligand Environment
journal contribution
posted on 2013-03-18, 00:00 authored by Matthew B. Chambers, Stanislav Groysman, Dino Villagrán, Daniel G. NoceraMononuclear
Fe(II) and Fe(III) complexes residing in a trigonal tris(ditox) (ditox
= tBu2(Me)CO–) ligand environment
have been synthesized and characterized. The Fe(III) ditox complex
does not react with oxidants such as PhIO, whereas NMe3O substitutes a coordinated tetrahydrofuran (THF) in the apical position
without undergoing oxo transfer. In contrast, the Fe(II) ditox complex
reacts rapidly with PhIO or Me3NO in THF or cyclohexadiene
to furnish a highly reactive intermediate, which cleaves C–H
bonds to afford the Fe(III)–hydroxide complex. When generated
in 1,2-difluorobenze, this intermediate can be intercepted to oxidize
phosphines to phosphine oxide. The fast rates at which these reactions
occur is attributed to a particularly weak ligand field imparted by
the tris(alkoxide) ancillary ligand environment.