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Amidophenolate Lanthanide Complexes and Their Multielectron Reactivity
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DOI：10.1021/acs.inorgchem.5c06116.png)
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Abstract
En 中文
A general approach to achieving multielectron reactivity with redox-restricted lanthanide complexes is to utilize redox-active ligands, which allow for facile electron transfer at the ligand throughout a reaction. Our group has successfully utilized an iminoquinone (iq) ligand capable of undergoing two-electron reduction events to form an iminosemiquinone (isq) and an amidophenolate (ap), respectively, on a variety of metals to achieve multielectron reactivity. Here, we report the synthesis and characterization of two tris-ligated lanthanide complexes, [Nd(ap)3]K3 (Nd-L3) and [Yb(ap)3]K3 (Yb-L3), and a bis-ligated complex, [Yb(ap)2]K (Yb-L2). Compounds Nd-L3 and Yb-L3 were treated with elemental sulfur. In the presence of S8, rapid ligand oxidation was observed, leading to the dissociation of a potassium iminosemiquinone ligand and the formation of a S72– chain. Alternatively, when S8 was added to Yb-L2, ligand oxidation was noted with the formation of a twist-boat metallocycle, [Yb(S5)(isq)2](K18c6) (Yb–S5). All complexes were fully characterized by using 1H NMR spectroscopy, electronic absorption spectroscopy, and X-ray crystallography to fully assign ligand oxidation states.
Keywords:
Lanthanides
Ligands
Oxidation
Redox reactions
Sulfur