title: Iron in a trigonal tris(alkoxide) ligand environment.
abstract: Mononuclear Fe(II) and Fe(III) complexes residing in a trigonal tris(ditox) (ditox = (t)Bu2(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.
authors: Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
authors: Matthew B
authors: MB
authors: Chambers
authors: Stanislav
authors: S
authors: Groysman
authors: Dino
authors: D
authors: Villagrán
authors: Daniel G
authors: DG
authors: Nocera