A μ-Phosphido Diiron Dumbbell in Multiple Oxidation States

A publication (journal article) of the University of Göttingen

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​A μ-Phosphido Diiron Dumbbell in Multiple Oxidation States​
Ghosh, M.; Cramer, H. H.; Dechert, S.; Demeshko, S.; John, M.; Hansmann, M. M. & Ye, S. et al.​ (2019) 
Angewandte Chemie International Edition58(40) pp. 14349​-14356​.​

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Authors
Ghosh, Munmun; Cramer, Hanna H.; Dechert, Sebastian; Demeshko, Serhiy; John, Michael; Hansmann, Max M.; Ye, Shengfa; Meyer, Franc
Abstract
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 μ-phosphido complex [(LFe)2 P](OTf)3 (3), which features an unprecedented linear Fe-(μ-P)-Fe motif and a "naked" P-atom bridge that appears at δ=+1480 ppm in the 31 P 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-(μ-P)-Fe core is highly covalent and structurally invariant over the series of oxidation states that are formally described as ranging from FeIII FeIII to FeIV FeIV . 3-5 now add a higher homologue set of complexes to the many systems with Fe-(μ-O)-Fe and Fe-(μ-N)-Fe core structures that are prominent in bioinorganic chemistry and catalysis.
Issue Date
2019
Journal
Angewandte Chemie International Edition 
Organization
Fakultät für Chemie 
ISBN
1350785
ISSN
1433-7851

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