Iron in a Trigonal Tris(alkoxide) Ligand Environment
2013-03-18T00:00:00Z (GMT)
by
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.
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