Synthesis and catalytic epoxidation activity with TBHP and H2O2 of dioxo-, oxoperoxo-, and oxodiperoxo molybdenum(VI) and tungsten(VI) compounds containing monodentate or bidentate phosphine oxide ligands: Crystal structures of WCl2(O)2 (OPMePh2)2, WCl2(O)(O2)(OPMePh2)2, MoCl2
Document Type
Article
Publication Date
12-11-2006
Department
Department of Chemistry
Abstract
The dioxo tungsten(VI) and molybdenum(VI) complexes WCl2(O) 2(OPMePh2)2, WCl2(O) 2dppmO2, and MoCl2(O)2-dppmO 2, the oxoperoxo compounds WCl2(O)(O2) (OPMePh2)2, WCl2(O)(O2)dppmO 2, and MoCl2(O)(O2)dppmO2, and the oxodiperoxo complexes, W(O)(O2)2dppmO2 and Mo(O)(O2)2dppmO2 have been prepared and characterized by IR spectroscopy, 31P NMR spectroscopy, elemental analysis, and X-ray crystallography. The structural and X-ray crystallographic data of compounds WCl2(O)2(OPMePh2) 2, WCl2(O)(O2)(OPMePh2)2, MoCl2(O)2dppmO2·C4H 10O, WCl2(O)2dppmO2, Mo(O)(O 2)2dppmO2, and W(O)(O2) 2dppmO2 are also detailed. All complexes were studied as catalysts for cis-cyclooctene epoxidation in the presence of tert-butyl hydroperoxide (TBHP) or H2O2 as an oxidant. The Mo-based catalysts showed a superior reactivity over W-based catalysts in the TBHP system. On the other hand, in the H2O2 system, the W-based catalysts (accomplishing nearly 100% epoxidation of cyclooctene in 6 h) are more reactive than the Mo catalysts ( < 45% under some conditions). Various solvent systems have been investigated, and ethanol is the most suitable solvent for the H2O2 system.
Publication Title
Inorganic Chemistry
Recommended Citation
Jimtaisong, A.,
&
Luck, R.
(2006).
Synthesis and catalytic epoxidation activity with TBHP and H2O2 of dioxo-, oxoperoxo-, and oxodiperoxo molybdenum(VI) and tungsten(VI) compounds containing monodentate or bidentate phosphine oxide ligands: Crystal structures of WCl2(O)2 (OPMePh2)2, WCl2(O)(O2)(OPMePh2)2, MoCl2.
Inorganic Chemistry,
45(25), 10391-10402.
http://doi.org/10.1021/ic061455d
Retrieved from: https://digitalcommons.mtu.edu/michigantech-p/7987