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The influences of carbon donor ligands on biomimetic multi-iron complexes for N₂ reduction.

ABSTRACT: The active site clusters of nitrogenase enzymes possess the only examples of carbides in biology. These are the only biological FeS clusters that are capable of reducing N₂ to NH₄ ⁺, implicating the central carbon and its interaction with Fe as important in the mechanism of N₂ reduction. This biological question motivates study of the influence of carbon donors on the electronic structure and reactivity of unsaturated, high-spin iron centers. Here, we present functional and structural models that test the impacts of carbon donors and sulfide donors in simpler iron compounds. We report the first example of a diiron complex that is bridged by an alkylidene and a sulfide, which serves as a high-fidelity structural and spectroscopic model of a two-iron portion of the active-site cluster (FeMoco) in the resting state of Mo-nitrogenase. The model complexes have antiferromagnetically coupled pairs of high-spin iron centers, and sulfur K-edge X-ray absorption spectroscopy shows comparable covalency of the sulfide for C and S bridged species. The sulfur-bridged compound does not interact with N₂ even upon reduction, but upon removal of the sulfide it becomes capable of reducing N₂ to NH₄ ⁺ with the addition of protons and electrons. This provides synthetic support for sulfide extrusion in the activation of nitrogenase cofactors.

SUBMITTER: Nagelski AL

PROVIDER: S-EPMC8163302 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

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The influences of carbon donor ligands on biomimetic multi-iron complexes for N2 reduction.

Nagelski Alexandra L AL Fataftah Majed S MS Bollmeyer Melissa M MM McWilliams Sean F SF MacMillan Samantha N SN Mercado Brandon Q BQ Lancaster Kyle M KM Holland Patrick L PL

Chemical science 20200806 47

The active site clusters of nitrogenase enzymes possess the only examples of carbides in biology. These are the only biological FeS clusters that are capable of reducing N2 to NH4 +, implicating the central carbon and its interaction with Fe as important in the mechanism of N2 reduction. This biological question motivates study of the influence of carbon donors on the electronic structure and reactivity of unsaturated, high-spin iron centers. Here, we ...[more]

PMID: 34094466

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Project description:The first use of a dinuclear UIII/UIII complex in the activation of small molecules is reported. The octadentate Schiff-base pyrrole, anthracene-hinged 'Pacman' ligand LA combines two strongly reducing UIII centres and three borohydride ligands in [M(THF)4][{U(BH4)}2(μ-BH4)(LA)(THF)2] 1-M, (M = Li, Na, K). The two borohydride ligands bound to uranium outside the macrocyclic cleft are readily substituted by aryloxide ligands, resulting in a single, weakly-bound, encapsulated endo group 1 metal borohydride bridging the two UIII centres in [{U(OAr)}2(μ-MBH4)(LA)(THF)2] 2-M (OAr = OC6H2t Bu3-2,4,6, M = Na, K). X-ray crystallographic analysis shows that, for 2-K, in addition to the endo-BH4 ligand the potassium counter-cation is also incorporated into the cleft through η5-interactions with the pyrrolides instead of extraneous donor solvent. As such, 2-K has a significantly higher solubility in non-polar solvents and a wider U-U separation compared to the 'ate' complex 1. The cooperative reducing capability of the two UIII centres now enforced by the large and relatively flexible macrocycle is compared for the two complexes, recognising that the borohydrides can provide additional reducing capability, and that the aryloxide-capped 2-K is constrained to reactions within the cleft. The reaction between 1-Na and S8 affords an insoluble, presumably polymeric paramagnetic complex with bridging uranium sulfides, while that with CS2 results in oxidation of each UIII to the notably high UV oxidation state, forming the unusual trithiocarbonate (CS3)2- as a ligand in [{U(CS3)}2(μ-κ2:κ2-CS3)(LA)] (4). The reaction between 2-K and S8 results in quantitative substitution of the endo-KBH4 by a bridging persulfido (S2)2- group and oxidation of each UIII to UIV, yielding [{U(OAr)}2(μ-κ2:κ2-S2)(LA)] (5). The reaction of 2-K with CS2 affords a thermally unstable adduct which is tentatively assigned as containing a carbon disulfido (CS2)2- ligand bridging the two U centres (6a), but only the mono-bridged sulfido (S)2- complex [{U(OAr)}2(μ-S)(LA)] (6) is isolated. The persulfido complex (5) can also be synthesised from the mono-bridged sulfido complex (6) by the addition of another equivalent of sulfur.

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The influences of carbon donor ligands on biomimetic multi-iron complexes for N₂ reduction.

Publications

The influences of carbon donor ligands on biomimetic multi-iron complexes for N<sub>2</sub> reduction.

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