Comparison of calix[n]arenes phosphorylated in the upper and lower rims as applied to extraction of nitrosoruthenium nitrite species

• Published in: Russian journal of inorganic chemistry Vol. 56; no. 3; pp. 473 - 478
• Main Authors: Torgov, V. G., Us, V. V., Korda, T. M., Kostin, G. A., Kal’chenko, V. I.
• Format: Journal Article
• Language: English
• Published: Dordrecht SP MAIK Nauka/Interperiodica 2011
• Subjects: Actinides; Chemistry; Chemistry and Materials Science; Constants; Extraction; Inorganic Chemistry; Mathematical analysis; Nitric acid; Oxides; Physical Chemistry of Solutions; Rims; Ruthenium; Americium; Ruthenium; High Level Waste; Phosphine Oxide; Extraction Constant
• ISSN: 0036-0236; 1531-8613
• DOI: 10.1134/S0036023611030223

Compared were dialkylcalix[4]phosphine oxides (L) having PO groups in the opposing rims as regards the extraction of [RuNO(NO 2 ) 4 (OH)] 2− , nonprecious metals (M 2+ ), and Ru/M heterometallic complexes of their base. The extraction constants for the ion association {(Na + ) 2 (LH 2 O) r [RuNO(NO 2 ) 4 (OH)] 2− and the degree of aggregation of L were calculated. The destruction of (LH 2 O) r upon metal extraction was verified IR-spectroscopically. The stoichiometry was determined and extraction constants were calculated for mono- and binuclear complexes [M m L n (NO 3 ) 2 m ] and mononuclear Ru/M species [RuNO(NO 2 ) 4 (OH)ML n ]. Nonprecious metals form mononuclear ML complexes in the lower rim. The size of the upper rim is responsible for the addition of a second metal nitrate molecule or addition to L or the addition of a second L molecule to the metal. Ru/M complexes with all L are present in an organic phase as two mononuclear species, ML and ML 2 . Rationale is given to the selection of extraction systems for recovery of ruthenium from nitrated nitric acid solutions selectively or together with actinides and lanthanides in the form of Ru/M complexes.