Iron in a Trigonal Tris(alkoxide) Ligand Environment
journal contributionposted on 18.03.2013 by Matthew B. Chambers, Stanislav Groysman, Dino Villagrán, Daniel G. Nocera
Any type of content formally published in an academic journal, usually following a peer-review process.
Mononuclear 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.