Synthesis of Iron(IV) Alkynylide Complexes and Their Reactivity to Form 1,3-Diynes.

Autor: Souilah C; Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany., Jannuzzi SAV; Max Planck Institute for Chemical Energy Conversion (MPI CEC), Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany., Becker FJ; Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany., Demirbas D; Max-Planck-Institut für Kohlenforschung (MPI KOFO), Kaiser-Wilhelm-Platz 1, 45470, Mülheim an der Ruhr, Germany., Jenisch D; Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany., Ivlev S; Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany., Xie X; Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany., Peredkov S; Max Planck Institute for Chemical Energy Conversion (MPI CEC), Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany., Lichtenberg C; Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany., DeBeer S; Max Planck Institute for Chemical Energy Conversion (MPI CEC), Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany., Casitas A; Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Nov 17, pp. e202421222. Date of Electronic Publication: 2024 Nov 17.
DOI: 10.1002/anie.202421222
Abstrakt: The isolation of thermally unstable and highly reactive organoiron(IV) complexes is a challenge for synthetic chemists. In particular, the number of examples where the C-based ligand is not part of the chelating ligand remains scarce. These compounds are of interest because they could pave the way to designing catalytic cycles of bond forming reactions proceeding via organoiron(IV) intermediates. Herein, we report the synthesis and characterization, including single-crystal X-ray diffraction, of a family of alkynylferrates(III) and Fe(IV) alkynylide complexes. The alkynylferrates(III) are formed by transmetalation of the Fe(III) precursor [(N 3 N')Fe III ] (N 3 N' 3- is tris(N-tert-butyldimethylsilyl-2-amidoethyl)amine) with lithium alkynylides, and their further one-electron oxidation enables the synthesis of the corresponding Fe(IV) alkynylides. The electronic structure of this family of organometallic Fe(III) and Fe(IV) complexes has been thoroughly investigated by spectroscopic methods (EPR, NMR, 57 Fe Mössbauer, X-Ray absorption (XAS) and emission (XES) spectroscopies) and theoretical calculations. While alkynylferrates(III) are sluggish to engage into C-C bond forming processes, the Fe(IV) alkynylides react to afford 1,3-diynes at room temperature. A bimolecular reductive elimination from a bimetallic Fe(IV) intermediate to form the 1,3-diynes is proposed based on the mechanistic investigations performed.
(© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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