Synthesis and lanthanide coordination chemistry of CMPO-decorated dibenzothiophene and dibenzothiophene sulfone platforms

Abstract

New hybrid donor ligands based on the dibenzothiophene and dibenzothiophene-5,5-dioxide platforms decorated with C-attached carbamoylmethylphosphine oxide substituents have been prepared. The potential chelation behavior of the ligands has been explored with molecular mechanics calculations and selected coordination chemistry with Ln(NO 3) 3 salts examined. The acid dependence of the solvent extraction performance of the dibenzothiophene-5,5-dioxide derivative for Am(III) and Eu(III) has also been surveyed.

Lanthanide phosphine oxide complexes

“…Solvent extraction studies showed that (36 X = SO 2 ) was better performing than (37 X = SO 2 ) [104] and that (37 X = O) is a stronger extractant than (36 X = O) [103]. Complexes of (38 X = S) (Ln = La, Pr, Eu, Er, Lu) are tetradentate on the basis of infrared spectroscopy in [Ln(NO 3 ) 3 (38)], whilst the coordination mode of (38 X = SO 2 ) is unclear due to overlap of bands in the spectra [105]. The crystal structure with X = SO shows that in [Eu(NO 3 ) 3 (38)], (38) bonds via both PO and the SO oxygen atoms with the amide carbonyl groups not bonded to the metal.…”

Ligands for f-element extraction used in the nuclear fuel cycle

“…Interestingly, DBT-6 was stable towards air oxidation, but underwent partial oxidation once coordinated with Ln(III) ions. 148…”

Synthesis and Properties of New (Phosphinoylmethyl)Pyridine N‐Oxides

“…A similar approach was recently employed in the assessment of chelate preferences for ligands derived from pyridine N-oxide platforms decorated with CMPO pendent arms. [18] Z. Anorg As a point of reference, the 1:1 binding of the parent NOPO fragment 3a on Gd III was evaluated, and a view of the lowest energy complexed form is shown in Figure 1a.…”