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Oxovanadium(V) complexes with tripodal bisphenolate and monophenolate ligands : Syntheses, structures and catalytic activities

Hossain, Md Kamal LU ; Haukka, Matti; Lisensky, George C. LU ; Lehtonen, Ari and Nordlander, Ebbe LU (2019) In Inorganica Chimica Acta 487. p.112-119
Abstract

The reactions between [VO(acac)2] (acac = acetylacetonate) and the tripodal amino bisphenols 6,6′-(((2-morpholinoethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) (H2L1) and 6,6′-(((thiophen-2-ylmethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) (H2L2) as well as the tetradentate amino phenol 2,2′-((3,5-di-tert-butyl-2-hydroxybenzyl)azanediyl)bis(ethan-1-ol) (H3L3) afford the complexes [VO(L1)(OMe)] (1), [VO(L2)(acac)] (2) and [VO(L3)] (3), correspondingly. Complexes 1 and 3 can also be prepared using VOSO4·xH2O or [VO(OPr)3] as vanadium precursors. When... (More)

The reactions between [VO(acac)2] (acac = acetylacetonate) and the tripodal amino bisphenols 6,6′-(((2-morpholinoethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) (H2L1) and 6,6′-(((thiophen-2-ylmethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) (H2L2) as well as the tetradentate amino phenol 2,2′-((3,5-di-tert-butyl-2-hydroxybenzyl)azanediyl)bis(ethan-1-ol) (H3L3) afford the complexes [VO(L1)(OMe)] (1), [VO(L2)(acac)] (2) and [VO(L3)] (3), correspondingly. Complexes 1 and 3 can also be prepared using VOSO4·xH2O or [VO(OPr)3] as vanadium precursors. When [VO(acac)2] or VOSO4·xH2O is used, mononuclear oxovanadium(V) complexes are formed upon oxidation of the metal precursor. Single crystal X-ray structure analysis show that complexes 1 and 2 have distorted octahedral coordination spheres, in which the amino bisphenolate coordinates in a tetradentate or tridentate manner, respectively, and the coordination spheres are completed by methoxy or acetylacetonato ligands. Complex 3 has a slightly distorted trigonal bipyramidal geometry with an NO4 coordination environment. All three complexes can catalyze epoxidation of cis-cyclooctene at 50 °C with tert-butyl hydroperoxide (TBHP) or H2O2 as an oxygen source, and sulfoxidation of thioanisole or methyl-p-tolylsulfide proceeds at 25 °C using the same oxidants.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
V NMR, DFT calculations, Epoxidation, Sulfoxidation, Vanadium(V) complexes
in
Inorganica Chimica Acta
volume
487
pages
8 pages
publisher
Elsevier
external identifiers
  • scopus:85058045447
ISSN
0020-1693
DOI
10.1016/j.ica.2018.11.049
language
English
LU publication?
yes
id
0185b4f2-2dd0-40ce-ac54-bb4cae9312b4
date added to LUP
2018-12-17 14:18:27
date last changed
2019-01-06 14:20:05
@article{0185b4f2-2dd0-40ce-ac54-bb4cae9312b4,
  abstract     = {<p>The reactions between [VO(acac)<sub>2</sub>] (acac<sup>–</sup> = acetylacetonate) and the tripodal amino bisphenols 6,6′-(((2-morpholinoethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) (H<sub>2</sub>L<sup>1</sup>) and 6,6′-(((thiophen-2-ylmethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) (H<sub>2</sub>L<sup>2</sup>) as well as the tetradentate amino phenol 2,2′-((3,5-di-tert-butyl-2-hydroxybenzyl)azanediyl)bis(ethan-1-ol) (H<sub>3</sub>L<sup>3</sup>) afford the complexes [VO(L<sup>1</sup>)(OMe)] (1), [VO(L<sup>2</sup>)(acac)] (2) and [VO(L<sup>3</sup>)] (3), correspondingly. Complexes 1 and 3 can also be prepared using VOSO<sub>4</sub>·xH<sub>2</sub>O or [VO(OPr)<sub>3</sub>] as vanadium precursors. When [VO(acac)<sub>2</sub>] or VOSO<sub>4</sub>·xH<sub>2</sub>O is used, mononuclear oxovanadium(V) complexes are formed upon oxidation of the metal precursor. Single crystal X-ray structure analysis show that complexes 1 and 2 have distorted octahedral coordination spheres, in which the amino bisphenolate coordinates in a tetradentate or tridentate manner, respectively, and the coordination spheres are completed by methoxy or acetylacetonato ligands. Complex 3 has a slightly distorted trigonal bipyramidal geometry with an NO<sub>4</sub> coordination environment. All three complexes can catalyze epoxidation of cis-cyclooctene at 50 °C with tert-butyl hydroperoxide (TBHP) or H<sub>2</sub>O<sub>2</sub> as an oxygen source, and sulfoxidation of thioanisole or methyl-p-tolylsulfide proceeds at 25 °C using the same oxidants.</p>},
  author       = {Hossain, Md Kamal and Haukka, Matti and Lisensky, George C. and Lehtonen, Ari and Nordlander, Ebbe},
  issn         = {0020-1693},
  keyword      = {V NMR,DFT calculations,Epoxidation,Sulfoxidation,Vanadium(V) complexes},
  language     = {eng},
  pages        = {112--119},
  publisher    = {Elsevier},
  series       = {Inorganica Chimica Acta},
  title        = {Oxovanadium(V) complexes with tripodal bisphenolate and monophenolate ligands : Syntheses, structures and catalytic activities},
  url          = {http://dx.doi.org/10.1016/j.ica.2018.11.049},
  volume       = {487},
  year         = {2019},
}