"Sweeping" Ortho Substituents Drive Desolvation and Overwhelm Electronic Effects in Nd Chelation: A Case of Three Aryldithiophosphinates.

08:00 EDT 9th September 2019 | BioPortfolio

Summary of ""Sweeping" Ortho Substituents Drive Desolvation and Overwhelm Electronic Effects in Nd Chelation: A Case of Three Aryldithiophosphinates."

Bis[-(trifluoromethyl)phenyl]dithiophosphinate is a sulfur-donating ligand capable of providing the largest reported trivalent lanthanide (Ln)-actinide (An) group separation factors. Literature has shown that the placement and number of the -CF functionalities on the aryl rings proximate to the ligating sulfur atoms can significantly impact Ln-An extraction and separation factors, but the complexation thermodynamics of -CF-derivatized aryldithiophosphinates have not been considered to date. This systematic study considers the complexation of three CF-substituted aryldithiophosphinates-bis(phenyl)dithiophosphinate (L), [-(trifluoromethyl)phenyl](phenyl)dithiophosphinate (L), and bis[-(trifluoromethyl)phenyl]dithiophosphinate (L), with Nd in an ethanolic environment. The chelating ability of Nd by these ligands follows the order of L > L > L, which is in line with the reported extraction efficiency. The positive Δ, as well as positive Δ, suggests that Nd chelation is entropy-driven and effective desolvation is critical to enabling Nd interaction with otherwise weakly interacting sulfur-containing ligands. Extended X-ray absorption fine structure results confirm thermodynamic investigations and suggest that L can only form up to 1:2 (M-L) complexes, while L and L form up to 1:3 complexes with Nd. All three L anions have bidentate interactions with Nd, but two L anions have bidentate interactions with Nd, while the third L anion is monodentate. The significant increase in Δ with each -CF addition suggests aiding desolvation could be central in enabling f-element interaction with weakly interacting donor groups, and this report provides an approach to controlling f-element desolvation as an innovative f-element chelating strategy.


Journal Details

This article was published in the following journal.

Name: Inorganic chemistry
ISSN: 1520-510X


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