Details

Autor(en) / Beteiligte

• Garhwal, Subhash
• Kaushansky, Alexander
• Fridman, Natalia
• Shimon, Linda J. W
• Ruiter, Graham de

Titel

Facile H/D Exchange at (Hetero)Aromatic Hydrocarbons Catalyzed by a Stable Trans-Dihydride N‑Heterocyclic Carbene (NHC) Iron Complex

Ist Teil von

• Journal of the American Chemical Society, 2020-10, Vol.142 (40), p.17131-17139

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2020

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Earth-abundant metal pincer complexes have played an important role in homogeneous catalysis during the last ten years. Yet, despite intense research efforts, the synthesis of iron PCcarbeneP pincer complexes has so far remained elusive. Here we report the synthesis of the first PCNHCP functionalized iron complex [(PCNHCP)­FeCl2] (1) and the reactivity of the corresponding trans-dihydride iron­(II) dinitrogen complex [(PCNHCP)­Fe­(H)2N2)] (2). Complex 2 is stable under an atmosphere of N2 and is highly active for hydrogen isotope exchange at (hetero)­aromatic hydrocarbons under mild conditions (50 °C, N2). With benzene-d 6 as the deuterium source, easily reducible functional groups such as esters and amides are well tolerated, contributing to the overall wide substrate scope (e.g., halides, ethers, and amines). DFT studies suggest a complex assisted σ-bond metathesis pathway for C­(sp2)–H bond activation, which is further discussed in this study.