Molybdenum (and/or tungsten) plays an essential role in all biological systems, as molybdenum oxo moieties are parts of the active sites of a number of metallenzymes, where they take part in oxo atom transfer chemistry.[1-3] Therefore, many molybdenum oxo complexes and their role in oxo transfer systems have been studied, in order to understand the mechanisms of enzymatic reactions. More recently, the chemistry of high valent rhenium(V) oxo complexes as corresponding bioinspired “artificial” oxotransfer reagents has received considerable attention.[4] Here we wish to report the results of the synthesis of a new cis-MoO22+ complex based on the tripodal ligand N-(2-hydroxybenzyl)-N-(2-picolyl)glycine (H2papy). In the solid state, the complex can be isolated as two different configurational isomers, viz. cis-trans-cis and all-cis, depending on the crystallization solvent as well as rhenium(V) oxo complexes of several tridentate phenolate hydrazone ligands (Scheme 1). All complexes were characterized by spectroscopic means as well as by single crystal X-ray diffraction analyses. All complexes were studied as catalyst for the oxo-transfer reactions and epoxidation reaction of several substrates with tBuOOH as well as H2O2.

Synthesis and reactivity studies of molybdenum(VI) and rhenium(V) oxo complexes as bioinspired oxo transfer catalysts

2019 Fall National Meeting

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