Back to Search
Start Over
Oxido-alcoholato/thiolato-molybdenum(VI) complexes with a dithiolene ligand generated by oxygen atom transfer to the molybdenum(IV) complexes
- Source :
- Inorganica Chimica Acta. 485:42-48
- Publication Year :
- 2019
- Publisher :
- Elsevier BV, 2019.
-
Abstract
- Oxido-alcoholato- and oxido-thiolato-molybdenum(VI) complexes bearing two ene-1,2-dithiolate ligands (cyclohexene-1,2-dithiolate) are prepared as synthetic models of molybdenum(VI) reaction centers of dimethyl sulfoxide reductase family of molybdenum enzymes. These complexes are prepared by oxygen atom transfer from tertiary amine N-oxide (trimethylamine N-oxide and N,N-dimethylaniline N-oxide) to the five-coordinate alcoholato- and thiolato-molybdenum(IV) complexes, and are characterized by UV–vis, cold-spray-ionization mass, resonance Raman, and 1H NMR spectroscopies. The oxygen atom transfer reactions are studied kinetically at a low temperature (−40 °C) to demonstrate that the reactivity of the thiolato-molybdenum(IV) complex is higher than that of alcoholato-molybdenum(IV) complex by about 7 times, and that the oxygen atom transfer reactivity increases with increasing the electron withdrawing ability of the p-substituent of N,N-dimethylaniline N-oxide derivatives. Mechanistic details are discussed based on the reactivity studies.
- Subjects :
- inorganic chemicals
Tertiary amine
010405 organic chemistry
Ligand
Trimethylamine
chemistry.chemical_element
010402 general chemistry
Resonance (chemistry)
01 natural sciences
0104 chemical sciences
Inorganic Chemistry
chemistry.chemical_compound
chemistry
Molybdenum
Polymer chemistry
Materials Chemistry
Proton NMR
Polar effect
bacteria
Reactivity (chemistry)
Physical and Theoretical Chemistry
Subjects
Details
- ISSN :
- 00201693
- Volume :
- 485
- Database :
- OpenAIRE
- Journal :
- Inorganica Chimica Acta
- Accession number :
- edsair.doi...........95ac4be0c63f2a89315fb3312b9dd488