Abstract
A sterically demanding molybdenum(VI) dioxo complex was found to catalytically activate molecular oxygen and to transfer its oxygen atoms to phosphines. Intermediate peroxo as well as reduced mono-oxo complexes were isolated and fully characterized. Monomeric Mo(IV) monooxo species proved to be of an unusual nature with the coordinated phosphine trans to the oxo group. The reduced molybdenum centers can activate O2 to form a stable Mo(VI) oxo-peroxo complex unambiguously characterized by single crystal X-ray diffraction analysis. NMR experiments demonstrate that both oxygen atoms of the peroxo unit are transferred to an accepting substrate, generating the Mo(IV) intermediate and restarting the catalytic cycle.
Highlights
High-valent molybdenum-oxo complexes are of considerable interest as catalysts for oxidation reactions.[1,2] In nature, molybdenum oxotransferases are a broad class of enzymes that transfer an oxygen atom to or from a substrate, using mainly water as a source of oxygen.[3]
In the course of our ongoing research on high-valent molybdenum-oxo complexes bearing Schiff-base ligands and their reactivity in oxygen atom transfer (OAT) reactions,[15,16,17] we report the synthesis and characterization of a new molybdenum(VI) dioxo complex which can be reduced and subsequently activate dioxygen to form a new molybdenum(VI) oxo–peroxo complex
We demonstrate that the molybdenum(VI) oxo–peroxo complex is active in OAT reaction and able to transfer both oxygen atoms of the peroxo moiety to an accepting substrate
Summary
High-valent molybdenum-oxo complexes are of considerable interest as catalysts for oxidation reactions.[1,2] In nature, molybdenum oxotransferases are a broad class of enzymes that transfer an oxygen atom to or from a substrate, using mainly water as a source of oxygen.[3]. This activation proceeds via the formation of a five-coordinated molybdenum(IV) mono-oxo complex or a highly unusual trans[MoO(PMe)3]2+ intermediate which was characterized by NMR spectroscopy and elemental analysis.
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