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Catalytic epoxidation using dioxidomolybdenum(VI) complexes with tridentate aminoalcohol phenol ligands

Hossain, Md Kamal LU ; Schachner, Jörg A.; Haukka, Matti; Mösch-Zanetti, Nadia C.; Nordlander, Ebbe LU and Lehtonen, Ari (2019) In Inorganica Chimica Acta 486. p.17-25
Abstract

Reaction of the tridentate aminoalcohol phenol ligands 2,4-di-tert-butyl-6-(((2 hydroxyethyl)(methyl)amino)methyl)phenol (H2L1) and 2,4-di-tert-butyl-6-(((1-hydroxybutan-2-yl)amino)methyl)phenol (H2L2) with [MoO2(acac)2] in methanol solutions resulted in the formation of [MoO2(L1)(MeOH)] (1) and [MoO2(L2)(MeOH)] (3), respectively. In contrast, the analogous reactions in acetonitrile afforded the dinuclear complexes [Mo2O2(μ-O)2(L1)2] (2) and [Mo2O2(μ-O)2(L2)2] (4). The corresponding reactions with the potentially... (More)

Reaction of the tridentate aminoalcohol phenol ligands 2,4-di-tert-butyl-6-(((2 hydroxyethyl)(methyl)amino)methyl)phenol (H2L1) and 2,4-di-tert-butyl-6-(((1-hydroxybutan-2-yl)amino)methyl)phenol (H2L2) with [MoO2(acac)2] in methanol solutions resulted in the formation of [MoO2(L1)(MeOH)] (1) and [MoO2(L2)(MeOH)] (3), respectively. In contrast, the analogous reactions in acetonitrile afforded the dinuclear complexes [Mo2O2(μ-O)2(L1)2] (2) and [Mo2O2(μ-O)2(L2)2] (4). The corresponding reactions with the potentially tetradentate ligand 3-((3,5-di-tert-butyl-2-hydroxybenzyl)(methyl)amino)propane-1,2-diol (H3L3) led to the formation of the mononuclear complex [MoO2(L3)(MeOH)] (5) in methanol while in acetonitrile solution a trinuclear structure [Mo3O3(μ-O)3(L3)3] (6) was obtained. In both cases, the ligand moiety L3 coordinated in a tridentate fashion. The catalytic activities of complexes 1–6 in epoxidation of five different olefins, S1-5, with tert-butyl hydroperoxide and hydrogen peroxide were studied. The catalytic activities were found to be moderate to good for the reaction of substrate cis-cyclooctene S1, while all complexes were less active in the epoxidation of the more challenging substrates S2-5. The molecular structures of 1, 2, 4 and 6 were determined by single crystal X-ray diffraction analyses.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Epoxidation, Molybdenum complex, Tridentate ligand, Trinuclear structure
in
Inorganica Chimica Acta
volume
486
pages
9 pages
publisher
Elsevier
external identifiers
  • scopus:85055113439
ISSN
0020-1693
DOI
10.1016/j.ica.2018.10.012
language
English
LU publication?
yes
id
4bf43a39-cf36-49e5-990f-6a778e7479a0
date added to LUP
2018-11-14 07:57:03
date last changed
2019-02-20 11:35:45
@article{4bf43a39-cf36-49e5-990f-6a778e7479a0,
  abstract     = {<p>Reaction of the tridentate aminoalcohol phenol ligands 2,4-di-tert-butyl-6-(((2 hydroxyethyl)(methyl)amino)methyl)phenol (H<sub>2</sub>L<sup>1</sup>) and 2,4-di-tert-butyl-6-(((1-hydroxybutan-2-yl)amino)methyl)phenol (H<sub>2</sub>L<sup>2</sup>) with [MoO<sub>2</sub>(acac)<sub>2</sub>] in methanol solutions resulted in the formation of [MoO<sub>2</sub>(L<sup>1</sup>)(MeOH)] (1) and [MoO<sub>2</sub>(L<sup>2</sup>)(MeOH)] (3), respectively. In contrast, the analogous reactions in acetonitrile afforded the dinuclear complexes [Mo<sub>2</sub>O<sub>2</sub>(μ-O)<sub>2</sub>(L<sup>1</sup>)<sub>2</sub>] (2) and [Mo<sub>2</sub>O<sub>2</sub>(μ-O)<sub>2</sub>(L<sup>2</sup>)<sub>2</sub>] (4). The corresponding reactions with the potentially tetradentate ligand 3-((3,5-di-tert-butyl-2-hydroxybenzyl)(methyl)amino)propane-1,2-diol (H<sub>3</sub>L<sup>3</sup>) led to the formation of the mononuclear complex [MoO<sub>2</sub>(L<sup>3</sup>)(MeOH)] (5) in methanol while in acetonitrile solution a trinuclear structure [Mo<sub>3</sub>O<sub>3</sub>(μ-O)<sub>3</sub>(L<sup>3</sup>)<sub>3</sub>] (6) was obtained. In both cases, the ligand moiety L<sup>3</sup> coordinated in a tridentate fashion. The catalytic activities of complexes 1–6 in epoxidation of five different olefins, S1-5, with tert-butyl hydroperoxide and hydrogen peroxide were studied. The catalytic activities were found to be moderate to good for the reaction of substrate cis-cyclooctene S1, while all complexes were less active in the epoxidation of the more challenging substrates S2-5. The molecular structures of 1, 2, 4 and 6 were determined by single crystal X-ray diffraction analyses.</p>},
  author       = {Hossain, Md Kamal and Schachner, Jörg A. and Haukka, Matti and Mösch-Zanetti, Nadia C. and Nordlander, Ebbe and Lehtonen, Ari},
  issn         = {0020-1693},
  keyword      = {Epoxidation,Molybdenum complex,Tridentate ligand,Trinuclear structure},
  language     = {eng},
  month        = {02},
  pages        = {17--25},
  publisher    = {Elsevier},
  series       = {Inorganica Chimica Acta},
  title        = {Catalytic epoxidation using dioxidomolybdenum(VI) complexes with tridentate aminoalcohol phenol ligands},
  url          = {http://dx.doi.org/10.1016/j.ica.2018.10.012},
  volume       = {486},
  year         = {2019},
}