Insights into the two‐electron reductive process of [FeFe]H2ase biomimetics. Cyclic voltammetry and DFT investigation on chelates control of redox properties of [Fe2(CO)4(κ2‐chelate)(µ‐dithiolate)]

Autor: Schollhammer, Philippe, Arrigoni, Federica, Elleouet, Catherine, Mele, Andrea, Pétillon, François, de Gioia, Luca, Zampella, Giuseppe
Přispěvatelé: Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Dipartimento di Biotecnologie e Bioscienze, Università degli Studi di Milano-Bicocca [Milano] (UNIMIB), Department of Biotechnologies and Biosciences, CNRS (Centre National de la Recherche Scientifique), the Université de Bretagne Occidentale, and the University of Milano-Bicocca are acknowledged for financial support., European Project: 675020,H2020,H2020-MSCA-ITN-2015,NoNoMeCat(2016), Schollhammer, P, Arrigoni, F, Elleouet, C, Mele, A, Pétillon, F, De Gioia, L, Zampella, G, 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), Università degli Studi di Milano-Bicocca = University of Milano-Bicocca (UNIMIB)
Jazyk: angličtina
Rok vydání: 2020
Předmět:
Zdroj: Chemistry-A European Journal
Chemistry-A European Journal, Wiley-VCH Verlag, 2020, ⟨10.1002/chem.202003233⟩
Chemistry-A European Journal, 2020, ⟨10.1002/chem.202003233⟩
ISSN: 0947-6539
1521-3765
DOI: 10.1002/chem.202003233⟩
Popis: International audience; The electrochemical reduction of complexes [Fe2(CO)4(k2‐phen)(μ‐xdt)] (phen = 1,10‐phenanthroline ; xdt = pdt (1), adtiPr (2)) in MeCN‐[Bu4N][PF6] 0.2 M is described as a two‐reduction process. DFT calculations show that 1 and its reduced form 1‐ display metal‐ and phenanthroline‐centered frontier orbitals (LUMO and SOMO) indicating the non‐innocence of the phenanthroline ligand. Two energetically close geometries were found for the doubly reduced species suggesting an intriguing influence of the phenanthroline ligand leading to the cleavage of a Fe‐S bond as proposed generally for this type of complex or retaining the electron density and avoiding Fe‐S cleavage. Extension of calculations to other complexes with edt, adtiPr bridge and even virtual species [Fe2(CO)4(k2‐phen)(μ‐adtR)] (R = CH(CF3)2, H) or [Fe2(CO)4(k2‐phen)(μ‐pdtR)] (R = CH(CF3)2, iPr) showed that the relative stability between both two‐electron‐reduced isomers depends on the nature of the bridge and the possibility to establish a remote anagostic interaction between the iron centre {Fe(CO)3} and the group carried by the bridged‐head atom of the dithiolate group.
Databáze: OpenAIRE
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