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Oxidovanadium(V) complexes with tridentate hydrazone ligands as oxygen atom transfer catalysts

Hossain, Md Kamal ; Haukka, Matti ; Lisensky, George C. LU ; Richmond, Michael G. and Nordlander, Ebbe LU (2024) In Polyhedron 258.
Abstract

Four isostructural oxovanadium(V) complexes with hydrazone ligands have been synthesised, characterised, and evaluated as epoxidation and sulfoxidation catalysts. The reactions between [VO(acac)2] (acac– = acetylacetonate) and H2Ln (n = 1–4), precursors for monoanionic tridentate hydrazone ligands, afford complexes formulated as [VO(Ln)(bzh)·MeOH] (1–4) when bidentate benzohydroxamic acid (Hbzh) is included as a co-ligand. Single crystal X-ray structure analyses showed that complexes 1–3 have a distorted octahedral coordination geometry with an O5N coordination environment. Cyclic voltammetry showed that all complexes undergo two quasi-irreversible reduction peaks and a... (More)

Four isostructural oxovanadium(V) complexes with hydrazone ligands have been synthesised, characterised, and evaluated as epoxidation and sulfoxidation catalysts. The reactions between [VO(acac)2] (acac– = acetylacetonate) and H2Ln (n = 1–4), precursors for monoanionic tridentate hydrazone ligands, afford complexes formulated as [VO(Ln)(bzh)·MeOH] (1–4) when bidentate benzohydroxamic acid (Hbzh) is included as a co-ligand. Single crystal X-ray structure analyses showed that complexes 1–3 have a distorted octahedral coordination geometry with an O5N coordination environment. Cyclic voltammetry showed that all complexes undergo two quasi-irreversible reduction peaks and a single irreversible oxidation peak. The bonding in 1 has been investigated by electronic structure calculations, and these data are discussed with respect to the electrochemical results. Complexes 1–4 were tested as catalysts for the epoxidation of cis-cyclooctene at 50 °C and sulfoxidation of methyl-p-tolylsulfide at room temperature using tert-butyl hydroperoxide (tBuOOH) and aqueous H2O2 as the terminal oxidants.

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author
; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
V NMR, DFT, Epoxidation, Hydrazone ligand, Sulfoxidation, Vanadium(V) complexes
in
Polyhedron
volume
258
article number
117020
publisher
Elsevier
external identifiers
  • scopus:85193067637
ISSN
0277-5387
DOI
10.1016/j.poly.2024.117020
language
English
LU publication?
yes
id
9fc8fc7e-1964-4827-835d-f7159f9883c8
date added to LUP
2024-05-27 15:49:28
date last changed
2024-05-30 12:47:28
@article{9fc8fc7e-1964-4827-835d-f7159f9883c8,
  abstract     = {{<p>Four isostructural oxovanadium(V) complexes with hydrazone ligands have been synthesised, characterised, and evaluated as epoxidation and sulfoxidation catalysts. The reactions between [VO(acac)<sub>2</sub>] (acac<sup>–</sup> = acetylacetonate) and H<sub>2</sub>L<sup>n</sup> (n = 1–4), precursors for monoanionic tridentate hydrazone ligands, afford complexes formulated as [VO(L<sup>n</sup>)(bzh)·MeOH] (1–4) when bidentate benzohydroxamic acid (Hbzh) is included as a co-ligand. Single crystal X-ray structure analyses showed that complexes 1–3 have a distorted octahedral coordination geometry with an O<sub>5</sub>N coordination environment. Cyclic voltammetry showed that all complexes undergo two quasi-irreversible reduction peaks and a single irreversible oxidation peak. The bonding in 1 has been investigated by electronic structure calculations, and these data are discussed with respect to the electrochemical results. Complexes 1–4 were tested as catalysts for the epoxidation of cis-cyclooctene at 50 °C and sulfoxidation of methyl-p-tolylsulfide at room temperature using tert-butyl hydroperoxide (tBuOOH) and aqueous H<sub>2</sub>O<sub>2</sub> as the terminal oxidants.</p>}},
  author       = {{Hossain, Md Kamal and Haukka, Matti and Lisensky, George C. and Richmond, Michael G. and Nordlander, Ebbe}},
  issn         = {{0277-5387}},
  keywords     = {{V NMR; DFT; Epoxidation; Hydrazone ligand; Sulfoxidation; Vanadium(V) complexes}},
  language     = {{eng}},
  publisher    = {{Elsevier}},
  series       = {{Polyhedron}},
  title        = {{Oxidovanadium(V) complexes with tridentate hydrazone ligands as oxygen atom transfer catalysts}},
  url          = {{http://dx.doi.org/10.1016/j.poly.2024.117020}},
  doi          = {{10.1016/j.poly.2024.117020}},
  volume       = {{258}},
  year         = {{2024}},
}