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An experimental and theoretical study of a heptacoordinated tungsten(VI) complex of a noninnocent phenylenediamine bis(phenolate) ligand

Hossain, Md Kamal LU ; Haukka, Matti ; Hänninen, Mikko M. ; Lisensky, George C. LU ; Paturi, Petriina ; Nordlander, Ebbe LU and Lehtonen, Ari (2018) In Inorganic Chemistry Communications 93. p.149-152
Abstract

[W(N2O2)(HN2O2)] (H4N2O2 = N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine) with a noninnocent ligand was formed by reaction of the alkoxide precursor [W(eg)3] (eg = the 1,2-ethanediolate dianion) with two equivalents of ligand. The phenol groups on one of the ligands are completely deprotonated and the ligand coordinates in a tetradentate fashion, whereas the other ligand is tridentate with one phenol having an intact OH group. The molecular structure, magnetic measurements, EPR spectroscopy, and density functional theory calculations indicate that the complex is a stable radical with the odd electron situated on the tridentate... (More)

[W(N2O2)(HN2O2)] (H4N2O2 = N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine) with a noninnocent ligand was formed by reaction of the alkoxide precursor [W(eg)3] (eg = the 1,2-ethanediolate dianion) with two equivalents of ligand. The phenol groups on one of the ligands are completely deprotonated and the ligand coordinates in a tetradentate fashion, whereas the other ligand is tridentate with one phenol having an intact OH group. The molecular structure, magnetic measurements, EPR spectroscopy, and density functional theory calculations indicate that the complex is a stable radical with the odd electron situated on the tridentate amidophenoxide ligand. The formal oxidation state of the metal center is W(VI), with the paramagnetic properties being due to the unpaired electron on the ligand.

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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Amidophenoxide radical, DFT calculations, Electronic structure, Noninnocent ligand, Oxidation states, Tungsten
in
Inorganic Chemistry Communications
volume
93
pages
4 pages
publisher
Elsevier
external identifiers
  • scopus:85047492675
ISSN
1387-7003
DOI
10.1016/j.inoche.2018.05.023
language
English
LU publication?
yes
id
e71d098c-e445-45f9-a9b1-6490c1786fb4
date added to LUP
2018-06-05 09:34:43
date last changed
2020-06-10 05:31:36
@article{e71d098c-e445-45f9-a9b1-6490c1786fb4,
  abstract     = {<p>[W(N<sub>2</sub>O<sub>2</sub>)(HN<sub>2</sub>O<sub>2</sub>)] (H<sub>4</sub>N<sub>2</sub>O<sub>2</sub> = N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine) with a noninnocent ligand was formed by reaction of the alkoxide precursor [W(eg)<sub>3</sub>] (eg = the 1,2-ethanediolate dianion) with two equivalents of ligand. The phenol groups on one of the ligands are completely deprotonated and the ligand coordinates in a tetradentate fashion, whereas the other ligand is tridentate with one phenol having an intact OH group. The molecular structure, magnetic measurements, EPR spectroscopy, and density functional theory calculations indicate that the complex is a stable radical with the odd electron situated on the tridentate amidophenoxide ligand. The formal oxidation state of the metal center is W(VI), with the paramagnetic properties being due to the unpaired electron on the ligand.</p>},
  author       = {Hossain, Md Kamal and Haukka, Matti and Hänninen, Mikko M. and Lisensky, George C. and Paturi, Petriina and Nordlander, Ebbe and Lehtonen, Ari},
  issn         = {1387-7003},
  language     = {eng},
  month        = {07},
  pages        = {149--152},
  publisher    = {Elsevier},
  series       = {Inorganic Chemistry Communications},
  title        = {An experimental and theoretical study of a heptacoordinated tungsten(VI) complex of a noninnocent phenylenediamine bis(phenolate) ligand},
  url          = {http://dx.doi.org/10.1016/j.inoche.2018.05.023},
  doi          = {10.1016/j.inoche.2018.05.023},
  volume       = {93},
  year         = {2018},
}