American Chemical Society
ic8b01259_si_001.pdf (2.17 MB)

Synthesis and Reactivity of Low-Valent f‑Element Iodide Complexes with Neutral Iminophosphorane Ligands

Download (2.17 MB)
journal contribution
posted on 2018-07-06, 16:19 authored by Thibault Cheisson, Louis Ricard, Frank W. Heinemann, Karsten Meyer, Audrey Auffrant, Grégory Nocton
The coordination and reactivity of simple iodide salts of low-valent f elements [YbI2, SmI2, TmI2, and UI3(THF)4, where THF = tetrahydrofuran] with iminophosphorane (R3PNR′) ligands are reported. The studied chelates were observed to adapt their geometry and effectively bind divalent ytterbium and samarium centers, as well as the trivalent uranium cation. The reactivity of the ytterbium adducts with benzophenone was found to be dependent on the steric demand of the supporting iminophosphorane ligand. In particular, a rare example of a stable charge-separated ketyl radical species is reported with ytterbium. Additionally, divalent thulium was observed to induce a reductive coupling at the ligand’s central pyridine ring.