Advanced

Dioxomolybdenum(VI) and -tungsten(VI) Complexes with Multidentate Aminobisphenol Ligands as Catalysts for Olefin Epoxidation

Dupe, Antoine; Hossain, Kamal LU ; Schachner, Joerg A.; Belaj, Ferdinand; Lehtonen, Ari; Nordlander, Ebbe LU and Moesch-Zanetti, Nadia C. (2015) In European Journal of Inorganic Chemistry p.3572-3579
Abstract
The synthesis of four molybdenum and tungsten complexes bearing tetradentate tripodal amino bisphenolate ligands with either hydroxyethylene (1a) or hydroxyglycolene (1b) substituents is reported. The molybdenum dioxo complexes [MoO2L] (L = 2a, 2b) and tungsten complexes [WO2L] (3a, 3b) were synthesized using [MoO2(acac)(2)] and [W(eg)(3)] (eg = 1,2-ethanediolato, ethylene glycolate), respectively, as precursors. All complexes were characterized by spectroscopic means as well as by single-crystal X-ray diffraction analyses. The latter reveal, in all cases, hexacoordinate complexes in which the hydrogen atom of the hydroxy group is involved in hydrogen bonding with one of the metal oxo groups. In the case of the glycol substituent, the... (More)
The synthesis of four molybdenum and tungsten complexes bearing tetradentate tripodal amino bisphenolate ligands with either hydroxyethylene (1a) or hydroxyglycolene (1b) substituents is reported. The molybdenum dioxo complexes [MoO2L] (L = 2a, 2b) and tungsten complexes [WO2L] (3a, 3b) were synthesized using [MoO2(acac)(2)] and [W(eg)(3)] (eg = 1,2-ethanediolato, ethylene glycolate), respectively, as precursors. All complexes were characterized by spectroscopic means as well as by single-crystal X-ray diffraction analyses. The latter reveal, in all cases, hexacoordinate complexes in which the hydrogen atom of the hydroxy group is involved in hydrogen bonding with one of the metal oxo groups. In the case of the glycol substituent, the ether oxygen atom is coordinated to the metal whereas the hydroxy group remains uncoordinated. The complexes were tested as catalysts in the epoxidation of cyclooctene under eco-friendly conditions, using an aqueous solution of H2O2 as the oxidant and dimethyl carbonate (DMC) as solvent or neat conditions, as substitutes for chlorinated solvents. Molybdenum complexes 2a and 2b showed good catalytic activity using H2O2 without added solvent, and tungsten complexes 3a and 3b showed very high activity in the epoxidation of cyclooctene using H2O2 and DMC as solvents. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Molybdenum, Tungsten, Hydrogen bonds, Epoxidation, Green chemistry
in
European Journal of Inorganic Chemistry
issue
21
pages
3572 - 3579
publisher
John Wiley & Sons
external identifiers
  • wos:000359297800022
  • scopus:84938214640
ISSN
1099-0682
DOI
10.1002/ejic.201500055
language
English
LU publication?
yes
id
eb660215-a725-4155-97f8-c6903a28f551 (old id 7975552)
date added to LUP
2015-09-24 15:09:45
date last changed
2017-11-19 03:17:32
@article{eb660215-a725-4155-97f8-c6903a28f551,
  abstract     = {The synthesis of four molybdenum and tungsten complexes bearing tetradentate tripodal amino bisphenolate ligands with either hydroxyethylene (1a) or hydroxyglycolene (1b) substituents is reported. The molybdenum dioxo complexes [MoO2L] (L = 2a, 2b) and tungsten complexes [WO2L] (3a, 3b) were synthesized using [MoO2(acac)(2)] and [W(eg)(3)] (eg = 1,2-ethanediolato, ethylene glycolate), respectively, as precursors. All complexes were characterized by spectroscopic means as well as by single-crystal X-ray diffraction analyses. The latter reveal, in all cases, hexacoordinate complexes in which the hydrogen atom of the hydroxy group is involved in hydrogen bonding with one of the metal oxo groups. In the case of the glycol substituent, the ether oxygen atom is coordinated to the metal whereas the hydroxy group remains uncoordinated. The complexes were tested as catalysts in the epoxidation of cyclooctene under eco-friendly conditions, using an aqueous solution of H2O2 as the oxidant and dimethyl carbonate (DMC) as solvent or neat conditions, as substitutes for chlorinated solvents. Molybdenum complexes 2a and 2b showed good catalytic activity using H2O2 without added solvent, and tungsten complexes 3a and 3b showed very high activity in the epoxidation of cyclooctene using H2O2 and DMC as solvents.},
  author       = {Dupe, Antoine and Hossain, Kamal and Schachner, Joerg A. and Belaj, Ferdinand and Lehtonen, Ari and Nordlander, Ebbe and Moesch-Zanetti, Nadia C.},
  issn         = {1099-0682},
  keyword      = {Molybdenum,Tungsten,Hydrogen bonds,Epoxidation,Green chemistry},
  language     = {eng},
  number       = {21},
  pages        = {3572--3579},
  publisher    = {John Wiley & Sons},
  series       = {European Journal of Inorganic Chemistry},
  title        = {Dioxomolybdenum(VI) and -tungsten(VI) Complexes with Multidentate Aminobisphenol Ligands as Catalysts for Olefin Epoxidation},
  url          = {http://dx.doi.org/10.1002/ejic.201500055},
  year         = {2015},
}