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Electronic fine-tuning of oxygen atom transfer reactivity of cis-dioxomolybdenum(VI) complexes with thiosemicarbazone ligands

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JournalEUROPEAN JOURNAL OF INORGANIC CHEMISTRY
DateE-pub ahead of print - 2 Apr 2015
DatePublished (current) - 2015
Number of pages10
Pages (from-to)3562-3571
Early online date2/04/15
Original languageEnglish

Abstract

A series of six cis-dioxomolybdenum(VI) complexes with thiosemicarbazone ligands was synthesized and characterized. The ligands were obtained by reacting ethyl thiosemicarbazide with salicylaldehydes substituted with a selection of electron-withdrawing and electron-donating groups. The crystal structures, IR, NMR spectroscopic data and oxygen atom transfer activities of the complexes revealed that the electronic effects of the substituents located in the para-position of the phenolate donor are transmitted through to the molybdenum center, as reflected by linear relationships between Hammett constants and key properties of the complexes, including the molybdenum-phenolate bond lengths and the coordination shift of the imine proton resonance. Compared with the unsubstituted catalyst, electron-withdrawing substituents increase the rate of oxygen atom transfer from dimethyl sulfoxide to triphenylphosphine, whereas electron-donating groups have the opposite effect. The highest rate enhancement was achieved through the introduction of a strongly electron-withdrawing NO2 substituent in the p-position of the phenolate donor.

    Research areas

  • Enzyme models, Ligand effects, Metalloenzymes, Molybdenum, Oxygen atom transfer

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