An experimental and theoretical study of a heptacoordinated tungsten(VI) complex of a noninnocent phenylenediamine bis(phenolate) ligand
(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
- Hossain, Md Kamal LU ; Haukka, Matti ; Hänninen, Mikko M. ; Lisensky, George C. LU ; Paturi, Petriina ; Nordlander, Ebbe LU and Lehtonen, Ari
- organization
- publishing date
- 2018-07-01
- 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
- 2022-04-02 00:38:04
@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}}, keywords = {{Amidophenoxide radical; DFT calculations; Electronic structure; Noninnocent ligand; Oxidation states; Tungsten}}, 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}}, }