Research output: Contribution to journal › Article › peer-review
Journal | EUROPEAN JOURNAL OF INORGANIC CHEMISTRY |
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Date | E-pub ahead of print - 2 Apr 2015 |
Date | Published (current) - 2015 |
Number of pages | 10 |
Pages (from-to) | 3562-3571 |
Early online date | 2/04/15 |
Original language | English |
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 output: Contribution to journal › Article › peer-review
Activity: Talk or presentation › Invited talk
Activity: Participating in or organising an event › Conference participation
Activity: Participating in or organising an event › Conference participation
Project: Research project (funded) › Research
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