A [3Fe–3S]<sup>3+</sup>cluster with exclusively μ-sulfide donors

Lee, Yousoon; Jeon, Ie‐Rang; Abboud, Khalil A.; García-Serres, Ricardo; Shearer, Jason; Murray, Leslie J.

doi:10.1039/c5cc07813j

Cited by 32 publications

(31 citation statements)

References 58 publications

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“…We have observed similar trends between iron(II) and iron(III) clusters supported by our ligand. 29,30 In agreement with a mixed-valent complex, a weak and broad absorption is observed in near-IR (NIR) spectra of solutions of 3 with λ max = 1117 nm. This feature is comparable to the intervalence charge-transfer band reported for the mixedvalent Fe III −N−Fe II reported by Brown et al 18 To validate the inclusion of an N atom within the cluster, we conducted protonolysis of 3, followed by quantification of the released nitrogen-containing ligand by the indophenol method.…”

Section: ■ Results and Discussionsupporting

confidence: 58%

Nitride-Bridged Triiron Complex and Its Relevance to Dinitrogen Activation

et al. 2015

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Using a simple metathesis approach, the triiron(II) tribromide complex Fe3Br3L (1) reacts with tetrabutylammonium azide to afford the monoazide dibromide analogue Fe3(Br)2(N3)L (2) in high yield. The inclusion of azide was confirmed by IR spectroscopy with a ν(N3) = 2082 cm(-1) as well as combustion analysis and X-ray crystallography. Heating 2 in the solid state results in the complete loss of the azide vibration in the IR spectra and the isolation of the olive-green mononitride complex Fe3(Br)2(N)L (3). Solution magnetic susceptibility measurements support that the trimetallic core within 2 is oxidized upon generation of 3 (5.07 vs 3.09 μB). Absorption maxima in the UV-visible-near-IR (NIR) spectra of 2 and 3 support the azide-to-nitride conversion, and a broad NIR absorption centered at 1117 nm is similar to that previously reported for the intervalence charge-transfer band for a mixed-valent nitridodiiron cluster. The cyclic voltammograms recorded for 3 are comparable to those of 1 with no reductive waves observed between ∼0 and -2.5 V (vs Fc/Fc(+)), whereas a reversible one-electron redox process is observed for Fe3(NH2)3L (4). These results suggest that intercluster cooperativity is unlikely to predominate the dinitrogen reduction mechanism when 1 is treated with KC8 under N2.

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Section: ■ Results and Discussionsupporting

confidence: 58%

Nitride-Bridged Triiron Complex and Its Relevance to Dinitrogen Activation

et al. 2015

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“…These parameters can also be tailored through molecular design. E.g., properly chosen ligand blends can force a low molecular symmetry that will also be reflected on the magnetic one, as has been shown in copper(II), 46 or iron(III) [47][48][49][50] triangles, with the latter type stabilizing S T = 5/2 ground states in cases of extreme distortions. 49,50 However, this criterion does not necessarily exclude high-symmetry…”

Section: Discussionmentioning

confidence: 97%

Polyanisotropic Magnetoelectric Coupling in an Electrically Controlled Molecular Spin Qubit

et al. 2019

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Two molecular spin qubits are studied with pulsed Electron Paramagnetic Resonance (EPR) spectroscopy under electric fields to assess their magnetoelectric (ME) couplings and electric spin control. [Fe 3 O(PhCOO) 6 (py) 3 ]ClO 4 ⋅py (Fe 3) is characterized by strong Dzyaloshinskii-Moriya interactions (DMI) which induce important magnetoanisotropy, whereas the DMI in [Cr 3 O(PhCOO) 6 (py) 3 ]ClO 4 ⋅0.5py (Cr 3) is 1-2 orders of magnitude weaker. Fe 3 is observed to demonstrate a clear ME effect whose intensity shows an unprecedented dependence on the molecular orientation within the electric field E (electroanisotropy) and on the relative orientations of the molecular z-axis, the Zeeman field B 0 and E (magnetoelectric anisotropy). The electric control in Fe 3 is shown to be coherent and the ME effect exhibits complex dynamics characterized by saturation and oscillatory effects. On the other hand, Cr 3 exhibits no discernible ME effect, which correlates well with its negligible DMI.

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“…The data presented here provide remarkable mechanistic detail of the conversion process. 3+ cluster has recently been described for the first time, in which all iron and sulfide ions are in the same molecular plane forming a hexagonal arrangement (31). Previous studies of the [3Fe-4S] cluster of FdI ferredoxin from Pyrococcus furiosus by nondenaturing ESI Fourier transform ion cyclotron resonance MS revealed the presence of a [3Fe-3S] 3+ cluster form along with other cluster breakdown species (26).…”

Section: Discussionmentioning

confidence: 99%

Mass spectrometric identification of intermediates in the O ₂ -driven [4Fe-4S] to [2Fe-2S] cluster conversion in FNR

Crack

Thomson

Brun

2017

Proc. Natl. Acad. Sci. U.S.A.

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The iron-sulfur cluster containing protein Fumarate and Nitrate Reduction (FNR) is the master regulator for the switch between anaerobic and aerobic respiration in and many other bacteria. The [4Fe-4S] cluster functions as the sensory module, undergoing reaction with O that leads to conversion to a [2Fe-2S] form with loss of high-affinity DNA binding. Here, we report studies of the FNR cluster conversion reaction using time-resolved electrospray ionization mass spectrometry. The data provide insight into the reaction, permitting the detection of cluster conversion intermediates and products, including a [3Fe-3S] cluster and persulfide-coordinated [2Fe-2S] clusters [[2Fe-2S](S) , where = 1 or 2]. Analysis of kinetic data revealed a branched mechanism in which cluster sulfide oxidation occurs in parallel with cluster conversion and not as a subsequent, secondary reaction to generate [2Fe-2S](S) species. This methodology shows great potential for broad application to studies of protein cofactor-small molecule interactions.

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A [3Fe–3S]³⁺cluster with exclusively μ-sulfide donors

Cited by 32 publications

References 58 publications

Nitride-Bridged Triiron Complex and Its Relevance to Dinitrogen Activation

Nitride-Bridged Triiron Complex and Its Relevance to Dinitrogen Activation

Polyanisotropic Magnetoelectric Coupling in an Electrically Controlled Molecular Spin Qubit

Mass spectrometric identification of intermediates in the O ₂ -driven [4Fe-4S] to [2Fe-2S] cluster conversion in FNR

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A [3Fe–3S]3+cluster with exclusively μ-sulfide donors

Cited by 32 publications

References 58 publications

Nitride-Bridged Triiron Complex and Its Relevance to Dinitrogen Activation

Nitride-Bridged Triiron Complex and Its Relevance to Dinitrogen Activation

Polyanisotropic Magnetoelectric Coupling in an Electrically Controlled Molecular Spin Qubit

Mass spectrometric identification of intermediates in the O 2 -driven [4Fe-4S] to [2Fe-2S] cluster conversion in FNR

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A [3Fe–3S]³⁺cluster with exclusively μ-sulfide donors

Mass spectrometric identification of intermediates in the O ₂ -driven [4Fe-4S] to [2Fe-2S] cluster conversion in FNR