Di- and Tetrairon(III) μ-Oxido Complexes of an N3S-Donor Ligand : Catalyst Precursors for Alkene Oxidations
Das, B., Al-Hunaiti, A., Sánchez-Eguía, B. N., Zeglio, E., Demeshko, S., Dechert, S., . . . Nordlander, E. (2019). Di- and Tetrairon(III) μ-Oxido Complexes of an N3S-Donor Ligand : Catalyst Precursors for Alkene Oxidations. Frontiers in Chemistry, 7, 97. doi:10.3389/fchem.2019.00097
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Frontiers in ChemistryAuthors
Date
2019Discipline
Epäorgaaninen ja analyyttinen kemiaCopyright
© 2019 The Authors.
The new di- and tetranuclear Fe(III) µ-oxido complexes
[Fe4(µ-O)4(PTEBIA)4](CF3SO3)4(CH3CN)2] (1a), [Fe2(µ-O)Cl2(PTEBIA)2](CF3SO3)2
(1b), and [Fe2(µ-O)(HCOO)2(PTEBIA)2](ClO4)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-toiron 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 H2O2/CH3COOH, with an absorption maximum at 410 nm. Homogeneous
oxidative catalytic activity was observed for 1a and 1b using H2O2 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.
...


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