Electronic and molecular structure relations in diiron compounds mimicking the [FeFe]-hydrogenase active site studied by X-ray spectroscopy and quantum chemistry
| Autor: | Sascha Ott, Michael Haumann, Nils Schuth, Daniel Daunke, Stefan Mebs, Florian Wittkamp, Michael Karnahl, Andreas Grohmann, Nils Leidel, Ulf-Peter Apfel, Frédéric Gloaguen, Ramona Kositzki, Lennart Schwartz |
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| Přispěvatelé: | Freie Universität Berlin, Angström Laboratory, Uppsala University, Ruhr-Universität Bochum [Bochum], Technische Universität Berlin (TU), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO) |
| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: |
Ligand field theory
X-ray absorption and emission spectroscopy [CHIM.INOR]Chemical Sciences/Inorganic chemistry 010402 general chemistry Photochemistry 01 natural sciences Quantum chemistry [FeFe]-hydrogenases Inorganic Chemistry Molecule Molecular orbital Alkyl density functional theory chemistry.chemical_classification Valence (chemistry) 010405 organic chemistry Chemistry 500 Naturwissenschaften und Mathematik::530 Physik::530 Physik 500 Naturwissenschaften und Mathematik::570 Biowissenschaften Biologie::570 Biowissenschaften Biologie 0104 chemical sciences Crystallography diiron compounds Density functional theory Electron configuration |
| Zdroj: | Dalton Transactions Dalton Transactions, Royal Society of Chemistry, 2017, 46 (37), pp.12544-12557. ⟨10.1039/C7DT02720F⟩ |
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.17169/refubium-1372 |
| Popis: | International audience; Synthetic diiron compounds of the general formula Fe2(μ-S2R)(CO)n(L)6−n (R = alkyl or aromatic groups; L = CN− or phosphines) are versatile models for the active-site cofactor of hydrogen turnover in [FeFe]-hydrogenases. A series of 18 diiron compounds, containing mostly a dithiolate bridge and terminal ligands of increasing complexity, was characterized by X-ray absorption and emission spectroscopy in combination with density functional theory. Fe K-edge absorption and Kβ main-line emission spectra revealed the varying geometry and the low-spin state of the Fe(I) centers. Good agreement between experimental and calculated core-to-valence-excitation absorption and radiative valence-to-core-decay emission spectra revealed correlations between spectroscopic and structural features and provided access to the electronic configuration. Four main effects on the diiron core were identified, which were preferentially related to variation either of the dithiolate or of the terminal ligands. Alteration of the dithiolate bridge affected mainly the Fe–Fe bond strength, while more potent donor substitution and ligand field asymmetrization changed the metal charge and valence level localization. In contrast, cyanide ligation altered all relevant properties and, in particular, the frontier molecular orbital energies of the diiron core. Mutual benchmarking of experimental and theoretical parameters provides guidelines to verify the electronic properties of related diiron compounds. |
| Databáze: | OpenAIRE |
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