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A mu-Phosphido Diiron Dumbbell in Multiple Oxidation States

MPG-Autoren
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Cramer,  Hanna H.
Research Department Leitner, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Zitation

Ghosh, M., Cramer, H. H., Dechert, S., Demeshko, S., John, M., Hansmann, M. M., et al. (2019). A mu-Phosphido Diiron Dumbbell in Multiple Oxidation States. Angewandte Chemie, International Edition in English, 58(40), 14349-14356. doi:10.1002/anie.201908213.


Zitierlink: https://hdl.handle.net/21.11116/0000-0005-DB86-D
Zusammenfassung
The reaction of the ferrous complex [LFe(NCMe)(2)](OTf)(2) (1), which contains a macrocyclic tetracarbene as ligand (L), with Na(OCP) generates the OCP--ligated complex [LFe(PCO)(CO)]OTf (2) together with the dinuclear mu-phosphido complex [(LFe)(2)P](OTf)(3) (3), which features an unprecedented linear Fe-(mu-P)-Fe motif and a "naked" P-atom bridge that appears at delta=+1480 ppm in the P-31 NMR spectrum. 3 exhibits rich redox chemistry, and both the singly and doubly oxidized species 4 and 5 could be isolated and fully characterized. X-ray crystallography, spectroscopic studies, in combination with DFT computations provide a comprehensive electronic structure description and show that the Fe-(mu-P)-Fe core is highly covalent and structurally invariant over the series of oxidation states that are formally described as ranging from (FeFeIII)-Fe-III to (FeFeIV)-Fe-IV. 3-5 now add a higher homologue set of complexes to the many systems with Fe-(mu-O)-Fe and Fe-(mu-N)-Fe core structures that are prominent in bioinorganic chemistry and catalysis.