The challenge of generating iron-sulfur clusters

Heim, Heiko C.; Bernhardt, Thorsten M.; Lang, Sandra M.

doi:10.1016/j.ijms.2015.07.009

Cited by 4 publications

(2 citation statements)

References 32 publications

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“…The experiment has been described in detail elsewhere and will be outlined only briefly here. 22 The iron−sulfur cluster cations were produced by sputtering pyrite stone targets 23 with high energetic Xe ions, which were generated in a cold reflex discharge ion source. 24 The cluster ion beam was steered into a helium-filled quadrupole ion guide to collimate and thermalize the hot clusters before mass selection in a first quadrupole mass filter.…”

Section: Methodsmentioning

confidence: 99%

Oxygen Sensitivity of Free Nonligated Iron–Sulfur Clusters

2019

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In view of the potential functionalization of iron−sulfur clusters as biomimetic catalysts, the oxygen sensitivity of these particles plays an important role.To gain fundamental insights into the interaction of iron−sulfur clusters with molecular oxygen, we employ free nonligated Fe x S x + (x = 2−6) clusters, that is, isolated iron−sulfur clusters without any additional ligands typically found in protein bound clusters, as well-defined model systems. Pressure-dependent gas phase ion trap experiments performed under multicollision conditions in conjunction with firstprinciples density functional theory simulations reveal the degradation of Fe 2 S 2 + via activation of O 2 to a superoxo species and subsequent thermodynamically favorable but kinetically hampered sequential exchange of the cluster sulfur atoms with oxygen atoms. A considerably faster exchange of multiple sulfur atoms is observed for Fe 3 S 3 + , Fe 5 S 5 + , and Fe 6 S 6 + in agreement with a kinetically and thermodynamically favored reaction mechanism, which involves the concerted exchange of two sulfur atoms of Fe 3 S 3 + . In marked contrast, Fe 4 S 4 + appears to be oxygen-tolerant and S/O exchange is not observed, which is attributed to an intrinsic weaker cluster−oxygen interaction.

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Section: Methodsmentioning

confidence: 99%

Oxygen Sensitivity of Free Nonligated Iron–Sulfur Clusters

2019

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“…The experimental setup to study the reactivity of the iron−sulfur clusters consists of a variabletemperature radiofrequency (rf)−octopole ion trap inserted into a low energy ion beam assembly. The iron−sulfur cluster cations are produced by sputtering pyrite stone targets 30 with high energetic Xe ions which are generated in a cold reflex discharge ion source (CORDIS). 31 The cluster ion beam is steered into a helium-filled quadrupole ion guide to collimate and thermalize the hot clusters before mass selection of the cluster size of interest in a first quadrupole mass filter.…”

Section: Methodsmentioning

confidence: 99%

Interaction of Iron–Sulfur Clusters with N₂: Biomimetic Systems in the Gas Phase

et al. 2016

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The active centers of the nitrogen-fixing enzymes nitrogenases comprise iron−sulfur clusters. The binding of the substrate N 2 to these clusters plays a fundamental role for the subsequent ammonia synthesis. However, due to the complexity of the natural system and the lack of suitable synthetic models, the interaction of N 2 with the iron−sulfur clusters remains largely elusive. In this contribution, we demonstrate the gas-phase preparation and investigation of the cationic Fe 2 S 2 + , Fe 3 S 3 + , and Fe 4 S 4 + clusters. These clusters represent the first cluster model systems containing more than one iron and sulfur atom, respectively, which are found to bind N 2 . Temperature-dependent kinetic measurements allow, for the first time, for the determination of experimental binding energies of N 2 to iron−sulfur clusters. In addition, concurrent firstprinciples simulations reveal the ground state and isomeric structures of the iron−sulfur clusters with and without adsorbed N 2 and provide a conceptual understanding of the interaction between N 2 and iron−sulfur clusters. In particular, we present molecular level details of N 2 bonding such as the identification of the adsorption sites, the bond geometry, the bond strength, and the nature of the cluster-N 2 binding interaction, which is found to be promoted by occupation of the empty antibonding orbitals of the free N 2 molecule through interaction with the frontier orbitals of the iron−sulfur complex involving d-orbitals of iron hybridized with sulfur porbitals.

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Tuning the oxidative power of free iron–sulfur clusters

Lang

Zhou

Schwarz

2017

Phys. Chem. Chem. Phys.

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The gas-phase reactions between a series of di-iron sulfur clusters FeS (x = 1-3) and the small alkenes CH, CH, and CH have been investigated by means of Fourier-transform ion-cyclotron resonance mass spectrometry. For all studied alkenes, the reaction efficiency is found to increase in the order FeS < FeS < FeS. In particular, FeS and FeS only form simple association products, whereas the sulfur-rich FeS is able to dehydrogenate propene and 2-butene via desulfurization of the cluster and formation of HS. This indicates an increased propensity to induce oxidation reactions, i.e. oxidative power, of FeS that is attributed to an increased formal oxidation state of the iron atoms. Furthermore, the ability of FeS to activate and dissociate the C-H bonds of the alkenes is observed to increase with increasing size of the alkene and thus correlates with the alkene ionization energy.

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The challenge of generating iron-sulfur clusters

Cited by 4 publications

References 32 publications

Oxygen Sensitivity of Free Nonligated Iron–Sulfur Clusters

Oxygen Sensitivity of Free Nonligated Iron–Sulfur Clusters

Interaction of Iron–Sulfur Clusters with N₂: Biomimetic Systems in the Gas Phase

Tuning the oxidative power of free iron–sulfur clusters

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The challenge of generating iron-sulfur clusters

Cited by 4 publications

References 32 publications

Oxygen Sensitivity of Free Nonligated Iron–Sulfur Clusters

Oxygen Sensitivity of Free Nonligated Iron–Sulfur Clusters

Interaction of Iron–Sulfur Clusters with N2: Biomimetic Systems in the Gas Phase

Tuning the oxidative power of free iron–sulfur clusters

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Resources

About

Interaction of Iron–Sulfur Clusters with N₂: Biomimetic Systems in the Gas Phase