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., Braunger, S., Haukka, M., Repo, T., Castillo, I., & Nordlander, E. (2019). Di- and Tetrairon(III) μ-Oxido Complexes of an N3S-Donor Ligand : Catalyst Precursors for Alkene Oxidations. Frontiers in Chemistry, 7, Article 97. https://doi.org/10.3389/fchem.2019.00097
Published in
Frontiers in ChemistryAuthors
Date
2019Copyright
© 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.
...


Publisher
Frontiers MediaISSN Search the Publication Forum
2296-2646Keywords
Publication in research information system
https://converis.jyu.fi/converis/portal/detail/Publication/28981756
Metadata
Show full item recordCollections
License
Related items
Showing items with similar title or keywords.
-
Highly Robust but Surface-Active : An N-Heterocyclic Carbene-Stabilized Au25 Nanocluster
Shen, Hui; Deng, Guocheng; Kaappa, Sami; Tan, Tongde; Han, Ying-Zi; Malola, Sami; Lin, Shui-Chao; Teo, Boon K.; Häkkinen, Hannu; Zheng, Nanfeng (Wiley-VCH Verlag, 2019)Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active ... -
Synthesis and Solid-State X-ray Structure of the Mononuclear Palladium(II) Complex Based on 1,2,3-Triazole Ligand
Al-Rasheed, Hessa H.; Haukka, Matti; Soliman, Saied M.; Al-Majid, Abdullah Mohammed; Ali, M.; El-Faham, Ayman; Barakat, Assem (MDPI AG, 2022)Herein, we described the synthesis and X-ray crystal structure of the new [Pd(3)2Cl2] complex with 1,2,3-triazole-based ligand (3). In the unit cell, there are two [Pd(3)2Cl2] molecules, and the asymmetric unit comprised ... -
A Next‐Generation Air‐Stable Palladium(I) Dimer Enables Olefin Migration and Selective C−C Coupling in Air
Kundu, Gourab; Sperger, Theresa; Rissanen, Kari; Schoenebeck, Franziska (Wiley-VCH Verlag, 2020)We report a new air‐stable PdI dimer, [Pd(μ‐I)(PCy2tBu)]2, which triggers E‐selective olefin migration to enamides and styrene derivatives in the presence of multiple functional groups and with complete tolerance of air. ... -
Dynamic Refolding of Ion-Pair Catalysts in Response to Different Anions
Neuvonen, Antti J.; Noutsias, Dimitris; Topić, Filip; Rissanen, Kari; Földes, Tamás; Pápai, Imre; Pihko, Petri M. (American Chemical Society, 2019)Four distinct folding patterns were identified in two foldamer-type urea-thiourea catalysts bearing a basic dimethylamino unit by a combination of X-ray crystallography, solution NMR studies, and computational studies ... -
Bimetallikompleksikatalyysi
Penttilä, Toni (2021)Tämän Pro Gradu -tutkielman kirjallisessa osassa käsitellään perinteisen metallikatalyysin pohjalta syntynyttä bimetallikatalyysiä, jossa joko kahdesta samasta tai eri siirtymämetallista koostuva kompleksi toimii reaktiivisena ...