Proton chelating ligands drive improved chemical separations for rhodium

成田 弘一*; Nicolson, R. M.*; 元川 竜平; 伊藤 文之*; 森作 員子*; 後藤 みどり*; 田中 幹也*; Heller, W. T.*; 塩飽 秀啓; 矢板 毅; et al.

Inorganic Chemistry, 58(13), p.8720 - 8734, 2019/07

https://doi.org/10.1021/acs.inorgchem.9b01136

Current industrial practices to extract rhodium from virgin ores carry a heavy environmental burden. Improving the efficiency of the hydrometallurgical processes to separate and recover rhodium from other precious metals provides an opportunity to improve the materials and energy balances, but the presence of mixed chloride-rhodium species following leaching by acid chloride media complicates the recovery process. In this work we have applied a broad range of analytical techniques (FT-IR spectroscopy, X-ray diffraction, EXAFS, water-transfer analysis, small-angle neutron scattering, NMR spectroscopy, and electrospray mass spectrometry), which together show that the amino-amide reagent preferentially transports chlorido-rhodium species as a 1:2 neutral assembly from aqueous 2.0 M HCl phase into an organic phase. The extractants then ligate in the outer coordination shell of the chloride-rhodium anion, making this an efficient separation process. In this study, we found that protonation to the extractants induced to form a proton chelate ring, which pre-organises the ligand to present an array of charge diffuse C-H bonds. This templated arrangement of positive dipoles favors complexation to the charge diffuse chloride-rhodium anion over the more charge-dense chloride anion.