Molybdenum-containing enzymes such as the DMSO reductase superfamily perform catalytic oxygen atom transfer. Biologically active molybdenum metal centers are most commonly chelated by sulfur-donating dithiolates, however the use of all-oxygen donor alkoxide ligands presents the opportunity to further explore how the first coordination sphere affects catalysis at the metal center. Efficient oxygen atom transfer in oxidation and epoxidation reactions is also of interest to industrial chemists. The Doerrer Research Group has previously utilized fluorinated alkoxides in order to stabilize first row transition metal complexes in high oxidation states. When paired with the bidentate fluorinated alkoxide (pinF)2-[n1] , reduced sensitivity to water is observed in a {V(pinF)} complex capable of oxidative dehydrogenation. (Inorg. Chem., 2020, 16500) This report will introduce the first examples of mono- and di- nuclear molybdenum coordination complexes bound by (pinF) and including Mo(V) and (VI) oxidation states. Characterization includes X-ray crystallography, UV-vis, multi-nuclear NMR, and FT-IR spectroscopies. The synthesis of these complexes is discussed as well as the initial substrate reactivity to test for oxygen atom transfer.

Synthesis and characterization of Mo(V) and Mo(VI) perfluorinated pinacolate complexes

ACS Spring Meeting 2021

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