期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 -, 期 21, 页码 3562-3571出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.201500059
关键词
Enzyme models; Metalloenzymes; Molybdenum; Oxygen atom transfer; Ligand effects
资金
- Engineering and Physical Sciences Research Council (EPSRC) [EP/J019666/1]
- COST Action [CM1003]
- University of York, UK
- Engineering and Physical Sciences Research Council [EP/J019666/1] Funding Source: researchfish
- EPSRC [EP/J019666/1] Funding Source: UKRI
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.
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