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A ?-Phosphido Diiron Dumbbell in Multiple Oxidation States.

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 ?-phosphido complex [(LFe)₂ P](OTf)₃ (3), which features an unprecedented linear Fe-(?-P)-Fe motif and a "naked" P-atom bridge that appears at ?=+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-(?-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-(?-O)-Fe and Fe-(?-N)-Fe core structures that are prominent in bioinorganic chemistry and catalysis.

SUBMITTER: Ghosh M

PROVIDER: S-EPMC6790664 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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A μ-Phosphido Diiron Dumbbell in Multiple Oxidation States.

Ghosh Munmun M Cramer Hanna H HH Dechert Sebastian S Demeshko Serhiy S John Michael M Hansmann Max M MM Ye Shengfa S Meyer Franc F

Angewandte Chemie (International ed. in English) 20190823 40

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 ...[more]

PMID: 31350785

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Project description:Progress toward the development of functional models of the carboxylate-bridged diiron active site in soluble methane monooxygenase is described in which potential substrates are introduced as substituents on bound pyridine ligands. Pyridine ligands incorporating a thiol, sulfide, sulfoxide, or phosphine moiety were allowed to react with the preassembled diiron(II) complex [Fe(2)(mu-O(2)CAr(R))(2)(O(2)CAr(R))(2)(THF)(2)], where (-)O(2)CAr(R) is a sterically hindered 2,6-di(p-tolyl)- or 2,6-di(p-fluorophenyl)benzoate (R = Tol or 4-FPh). The resulting diiron(II) complexes were characterized crystallographically. Triply and doubly bridged compounds [Fe(2)(mu-O(2)CAr(Tol))(3)(O(2)CAr(Tol))(2-MeSpy)] (4) and [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(2-MeS(O)py)(2)] (5) resulted when 2-methylthiopyridine (2-MeSpy) and 2-pyridylmethylsulfoxide (2-MeS(O)py), respectively, were employed. Another triply bridged diiron(II) complex, [Fe(2)(mu-O(2)CAr(4)(-)(FPh))(3)-(O(2)CAr(4)(-)(FPh))(2-Ph(2)Ppy)] (3), was obtained containing 2-diphenylphosphinopyridine (2-Ph(2)Ppy). The use of 2-mercaptopyridine (2-HSpy) produced the mononuclear complex [Fe(O(2)CAr(Tol))(2)(2-HSpy)(2)] (6a). Together with that of previously reported [Fe(2)(mu-O(2)CAr(Tol))(3)(O(2)CAr(Tol))(2-PhSpy)] (2) and [Fe(2)(mu-O(2)CAr(Tol))(3)(O(2)CAr(Tol))(2-Ph(2)Ppy)] (1), the dioxygen reactivity of these iron(II) complexes was investigated. A dioxygen-dependent intermediate (6b) formed upon exposure of 6a to O(2), the electronic structure of which was probed by various spectroscopic methods. Exposure of 4 and 5 to dioxygen revealed both sulfide and sulfoxide oxidation. Oxidation of 3 in CH(2)Cl(2) yields [Fe(2)(mu-OH)(2)(mu-O(2)CAr(4)(-)(FPh))(O(2)CAr(4)(-FPh))(3)(OH(2))(2-Ph(2)P(O)py)] (8), which contains the biologically relevant {Fe(2)(mu-OH)(2)(mu-O(2)CR)}(3+) core. This reaction is sensitive to the choice of carboxylate ligands, however, since the p-tolyl analogue 1 yielded a hexanuclear species, 7, upon oxidation.

Dataset Information

A ?-Phosphido Diiron Dumbbell in Multiple Oxidation States.

Publications

A μ-Phosphido Diiron Dumbbell in Multiple Oxidation States.

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