Abstract
Low-valent iron centers are critical intermediates in chemical and bio-chemical processes. Herein, we show the first example of a low-valent FeI center stabilized in a high-valent polyoxometalate framework. Electrochemical studies show that the FeIII-functionalized molecular vanadium(V) oxide (DMA)[FeIIIClVV 12O32Cl]3− (DMA=dimethylammonium) features two well-defined, reversible, iron-based electrochemical reductions which cleanly yield the FeI species (DMA)[FeIClVV 12O32Cl]5−. Experimental and theoretical studies including electron paramagnetic resonance spectroscopy and density functional theory computations verify the formation of the FeI species. The study presents the first example for the seemingly paradoxical embedding of low-valent metal species in high-valent metal oxide anions and opens new avenues for reductive electron transfer catalysis by polyoxometalates.
| Original language | English |
|---|---|
| Pages (from-to) | 14749-14752 |
| Number of pages | 4 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 56 |
| Issue number | 46 |
| DOIs | |
| Publication status | Published - 13 Nov 2017 |
Keywords
- electrochemistry
- iron
- metal oxides
- polyoxometalates
- self-assembly
Cite this
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Stabilization of Low-Valent Iron(I) in a High-Valent Vanadium(V) Oxide Cluster. / Anjass, Montaha H.; Kastner, Katharina; Nägele, Florian; Ringenberg, Mark; Boas, John F.; Zhang, Jie; Bond, Alan M.; Jacob, Timo; Streb, Carsten.
In: Angewandte Chemie - International Edition, Vol. 56, No. 46, 13.11.2017, p. 14749-14752.Research output: Contribution to journal › Article › Research › peer-review
TY - JOUR
T1 - Stabilization of Low-Valent Iron(I) in a High-Valent Vanadium(V) Oxide Cluster
AU - Anjass, Montaha H.
AU - Kastner, Katharina
AU - Nägele, Florian
AU - Ringenberg, Mark
AU - Boas, John F.
AU - Zhang, Jie
AU - Bond, Alan M.
AU - Jacob, Timo
AU - Streb, Carsten
PY - 2017/11/13
Y1 - 2017/11/13
N2 - Low-valent iron centers are critical intermediates in chemical and bio-chemical processes. Herein, we show the first example of a low-valent FeI center stabilized in a high-valent polyoxometalate framework. Electrochemical studies show that the FeIII-functionalized molecular vanadium(V) oxide (DMA)[FeIIIClVV 12O32Cl]3− (DMA=dimethylammonium) features two well-defined, reversible, iron-based electrochemical reductions which cleanly yield the FeI species (DMA)[FeIClVV 12O32Cl]5−. Experimental and theoretical studies including electron paramagnetic resonance spectroscopy and density functional theory computations verify the formation of the FeI species. The study presents the first example for the seemingly paradoxical embedding of low-valent metal species in high-valent metal oxide anions and opens new avenues for reductive electron transfer catalysis by polyoxometalates.
AB - Low-valent iron centers are critical intermediates in chemical and bio-chemical processes. Herein, we show the first example of a low-valent FeI center stabilized in a high-valent polyoxometalate framework. Electrochemical studies show that the FeIII-functionalized molecular vanadium(V) oxide (DMA)[FeIIIClVV 12O32Cl]3− (DMA=dimethylammonium) features two well-defined, reversible, iron-based electrochemical reductions which cleanly yield the FeI species (DMA)[FeIClVV 12O32Cl]5−. Experimental and theoretical studies including electron paramagnetic resonance spectroscopy and density functional theory computations verify the formation of the FeI species. The study presents the first example for the seemingly paradoxical embedding of low-valent metal species in high-valent metal oxide anions and opens new avenues for reductive electron transfer catalysis by polyoxometalates.
KW - electrochemistry
KW - iron
KW - metal oxides
KW - polyoxometalates
KW - self-assembly
UR - http://www.scopus.com/inward/record.url?scp=85030671036&partnerID=8YFLogxK
U2 - 10.1002/anie.201706828
DO - 10.1002/anie.201706828
M3 - Article
VL - 56
SP - 14749
EP - 14752
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 46
ER -