3 years ago

Stabilization of Low-Valent Iron(I) in a High-Valent Vanadium(V) Oxide Cluster

Stabilization of Low-Valent Iron(I) in a High-Valent Vanadium(V) Oxide Cluster
Montaha H. Anjass, Mark Ringenberg, Jie Zhang, John F. Boas, Katharina Kastner, Carsten Streb, Timo Jacob, Alan M. Bond, Florian Nägele
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)[FeIIIClVV12O32Cl]3− (DMA=dimethylammonium) features two well-defined, reversible, iron-based electrochemical reductions which cleanly yield the FeI species (DMA)[FeIClVV12O32Cl]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. Iron in: The electrochemical formation and stabilization of a low-valent iron(I) center within a high-valent, molecular vanadium(V) oxide cluster gives (NH2Me2)[FeIClVV12O32Cl]5−. Experimental and theoretical studies provide insight into the electronic structure, reactivity, and stability of the species. The study opens new pathways for isolating and stabilizing low-valent transition-metal centers in high-valent polyoxometalate clusters.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201706828

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