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Access to Metal Centers and Fluxional Hydride Coordination Integral for CO₂ Insertion into [Fe₃(μ-H)₃]³⁺ Clusters.

ABSTRACT: CO₂ insertion into tri(μ-hydrido)triiron(II) clusters ligated by a tris(β-diketiminate) cyclophane is demonstrated to be balanced by sterics for CO₂ approach and hydride accessibility. Time-resolved NMR and UV-vis spectra for this reaction for a complex in which methoxy groups border the pocket of the hydride donor (Fe₃H₃L², 4) result in a decreased activation barrier and increased kinetic isotope effect consistent with the reduced sterics. For the ethyl congener Fe₃H₃L¹ (2), no correlation is found between rate and reaction solvent or added Lewis acids, implying CO₂ coordination to an Fe center in the mechanism. The estimated hydricity (50 kcal/mol) based on observed H/D exchange with BD₃ requires Fe-O bond formation in the product to offset an endergonic CO₂ insertion. μ₃-hydride coordination is noted to lower the activation barrier for the first CO₂ insertion event in DFT calculations.

SUBMITTER: Hong DH

PROVIDER: S-EPMC8247455 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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Access to Metal Centers and Fluxional Hydride Coordination Integral for CO2 Insertion into [Fe3(μ-H)3]3+ Clusters.

Hong Dae Ho DH Ferreira Ricardo B RB Catalano Vincent J VJ García-Serres Ricardo R Shearer Jason J Murray Leslie J LJ

Inorganic chemistry 20210426 10

CO2 insertion into tri(μ-hydrido)triiron(II) clusters ligated by a tris(β-diketiminate) cyclophane is demonstrated to be balanced by sterics for CO2 approach and hydride accessibility. Time-resolved NMR and UV-vis spectra for this reaction for a complex in which methoxy groups border the pocket of the hydride donor (Fe3H3L2, 4) result in a decreased activation barrier and increased kinetic isotope effect consistent with ...[more]

PMID: 33900076

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Project description:The mixed-valence triiron complexes [Fe3(CO)7-x (PPh3) x (μ-edt)2] (x = 0-2; edt = SCH2CH2S) and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2] (diphosphine = dppv, dppe, dppb, dppn) have been prepared and structurally characterized. All adopt an anti arrangement of the dithiolate bridges, and PPh3 substitution occurs at the apical positions of the outer iron atoms, while the diphosphine complexes exist only in the dibasal form in both the solid state and solution. The carbonyl on the central iron atom is semibridging, and this leads to a rotated structure between the bridged diiron center. IR studies reveal that all complexes are inert to protonation by HBF4·Et2O, but addition of acid to the pentacarbonyl complexes results in one-electron oxidation to yield the moderately stable cations [Fe3(CO)5(PPh3)2(μ-edt)2]+ and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2]+, species which also result upon oxidation by [Cp2Fe][PF6]. The electrochemistry of the formally Fe(I)-Fe(II)-Fe(I) complexes has been investigated. Each undergoes a quasi-reversible oxidation, the potential of which is sensitive to phosphine substitution, generally occurring between 0.15 and 0.50 V, although [Fe3(CO)5(PPh3)2(μ-edt)2] is oxidized at -0.05 V. Reduction of all complexes is irreversible and is again sensitive to phosphine substitution, varying between -1.47 V for [Fe3(CO)7(μ-edt)2] and around -1.7 V for phosphine-substituted complexes. In their one-electron-reduced states, all complexes are catalysts for the reduction of protons to hydrogen, the catalytic overpotential being increased upon successive phosphine substitution. In comparison to the diiron complex [Fe2(CO)6(μ-edt)], [Fe3(CO)7(μ-edt)2] catalyzes proton reduction at 0.36 V less negative potentials. Electronic structure calculations have been carried out in order to fully elucidate the nature of the oxidation and reduction processes. In all complexes, the HOMO comprises an iron-iron bonding orbital localized between the two iron atoms not ligated by the semibridging carbonyl, while the LUMO is highly delocalized in nature and is antibonding between both pairs of iron atoms but also contains an antibonding dithiolate interaction.

Dataset Information

Access to Metal Centers and Fluxional Hydride Coordination Integral for CO₂ Insertion into [Fe₃(μ-H)₃]³⁺ Clusters.

Publications

Access to Metal Centers and Fluxional Hydride Coordination Integral for CO<sub>2</sub> Insertion into [Fe<sub>3</sub>(μ-H)<sub>3</sub>]<sup>3+</sup> Clusters.

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