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Issue 41, 2015
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19F NMR study of ligand dynamics in carboxylate-bridged diiron(II) complexes supported by a macrocyclic ligand

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Abstract

A series of asymmetrically carboxylate-bridged diiron(II) complexes featuring fluorine atoms as NMR spectroscopic probes, [Fe2(PIM)(Ar4F-PhCO2)2] (10), [Fe2(F2PIM)(ArTolCO2)2] (11), and [Fe2(F2PIM)(Ar4F-PhCO2)2] (12), were prepared and characterized by X-ray crystallography, Mössbauer spectroscopy, and VT 19F NMR spectroscopy. These complexes are part of a rare family of syn N-donor diiron(II) compounds, [Fe2(X2PIM)(RCO2)2], that are structurally very similar to the active site of the hydroxylase enzyme component of reduced methane monooxygenase (MMOHred). Solution characterization of these complexes demonstrates that they undergo intramolecular carboxylate rearrangements, or carboxylate shifts, a dynamic feature relevant to the reactivity of the diiron centers in bacterial multicomponent monooxygenases.

Graphical abstract: 19F NMR study of ligand dynamics in carboxylate-bridged diiron(ii) complexes supported by a macrocyclic ligand

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Publication details

The article was received on 05 Jun 2015, accepted on 26 Aug 2015 and first published on 29 Sep 2015


Article type: Paper
DOI: 10.1039/C5DT02138C
Citation: Dalton Trans., 2015,44, 18111-18121
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    19F NMR study of ligand dynamics in carboxylate-bridged diiron(II) complexes supported by a macrocyclic ligand

    M. A. Minier and S. J. Lippard, Dalton Trans., 2015, 44, 18111
    DOI: 10.1039/C5DT02138C

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