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Ebbe Nordlander. Portrait.

Ebbe Nordlander

Professor

Ebbe Nordlander. Portrait.

Di- and tetrairon(III) μ-oxido complexes of an N3S-donor ligand : Catalyst precursors for alkene oxidations

Author

  • Biswanath Das
  • Afnan Al-Hunaiti
  • Brenda N. Sánchez-Eguía
  • Erica Zeglio
  • Serhiy Demeshko
  • Sebastian Dechert
  • Steffen Braunger
  • Matti Haukka
  • Timo Repo
  • Ivan Castillo
  • Ebbe Nordlander
Show all

Summary, in English


The new di- and tetranuclear Fe(III) μ-oxido complexes [Fe
4
(μ-O)
4
(PTEBIA)
4
](CF
3
SO
3
)
4
(CH
3
CN)
2
] (1a), [Fe
2
(μ-O)Cl
2
(PTEBIA)
2
](CF
3
SO
3
)
2
(1b), and [Fe
2
(μ-O)(HCOO)
2
(PTEBIA)
2
](ClO
4
)
2
(MeOH) (2) were prepared from the sulfur-containing ligand (2-((2,4-dimethylphenyl)thio)-N,N-bis ((1-methyl-benzimidazol-2-yl)methyl)ethanamine (PTEBIA). The tetrairon complex 1a features four μ-oxido bridges, while in dinuclear 1b, the sulfur moiety of the ligand occupies one of the six coordination sites of each Fe(III) ion with a long Fe-S distance of 2.814(6) Å. In 2, two Fe(III) centers are bridged by one oxido and two formate units, the latter likely formed by methanol oxidation. Complexes 1a and 1b show broad sulfur-to-iron charge transfer bands around 400-430 nm at room temperature, consistent with mononuclear structures featuring Fe-S interactions. In contrast, acetonitrile solutions of 2 display a sulfur-to-iron charge transfer band only at low temperature (228 K) upon addition of H
2
O
2
/CH
3
COOH, with an absorption maximum at 410 nm. Homogeneous oxidative catalytic activity was observed for 1a and 1b using H
2
O
2
as oxidant, but with low product selectivity. High valent iron-oxo intermediates could not be detected by UV-vis spectroscopy or ESI mass spectrometry. Rather, evidence suggest preferential ligand oxidation, in line with the relatively low selectivity and catalytic activity observed in the reactions.

Department/s

  • Chemical Physics

Publishing year

2019-03-01

Language

English

Publication/Series

Frontiers in Chemistry

Volume

7

Issue

MAR

Document type

Journal article

Publisher

Frontiers Media S. A.

Topic

  • Inorganic Chemistry

Keywords

  • Fe-S interaction
  • Homogeneous catalysis
  • Iron-oxo complex
  • Oxidation
  • Thioether

Status

Published

ISBN/ISSN/Other

  • ISSN: 2296-2646