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A μ‐Phosphido Diiron Dumbbell in Multiple Oxidation States
Author(s) -
Ghosh Munmun,
Cramer Hanna H.,
Dechert Sebastian,
Demeshko Serhiy,
John Michael,
Hansmann Max M.,
Ye Shengfa,
Meyer Franc
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201908213
Subject(s) - chemistry , dumbbell , crystallography , bioinorganic chemistry , redox , ferrous , ligand (biochemistry) , covalent bond , stereochemistry , inorganic chemistry , organic chemistry , receptor , physical therapy , medicine , biochemistry
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 Fe III Fe III to Fe IV Fe IV . 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.