Study of lithium complexes with benzo-15-crown-5 ether by X-ray diffraction and IR spectroscopy

The complex formation of lithium with benzo-15-crown-5 (B15C5) was investigated. The complexes LiB15C5H₂OX, where X = Cl^? (1), I^? (2), (3), (5), and LiBF₄B15C5 (4) were synthesized and studied by IR spectroscopy. Complexes 1–4 were examined by X-ray diffraction. According to IR spectroscopy data, the crown ether conformation changes upon dissolution. The interaction of the extracted complex with the solvent was identified.     

Effects of Side-Chain Substituents in Benzo-15-Crown-5 on Lithium Extraction

Chloroform–water extraction systems have been studied using crown-ethers as extracting agents, namely: benzo-15-crown-5 (B15C5), 2,3-naphtho-15-crown-5 (N15C5), 4′-nitro-benzo-15-crown-5 (NO₂B15C5), 4′-tert-butyl-benzo-15-crown-5 (TBB15C5), and 4′-acetyl-benzo-15-crown-5 (AcB15C5). Extraction isotherms of these systems have been obtained, and an attempt made to elucidate the effect of the structure of extracting agent on extraction characteristics. IR-spectroscopic studies have been performed for selected crown-ethers and their complexes in crystalline form and in chloroform solutions, namely, for N15C5, NO₂B15C5, AcB15C5, and B15C5. The complexes LiN15C5H₂OClO₄ (1), LiN15C5H₂OI (2), LiNO₂B15C5H₂OI (3), LiAcB15C5H₂OI (4), and LiTBB15C5H₂OI (5) have been isolated for the first time and characterized by IR spectroscopy. Single-crystal X-ray data have been obtained for complexes 1–3.     

Molecular design of macrocyclic extractants for extraction and separation of alkali and alkaline-earth metals

The distribution coefficients of the alkaline and alkali-earth metal nitrates are determined for the processes of extraction from nitric acid solutions with crown ethers, which differ in sizes of their cycles (from 18 to 22 atoms) and in side phenyl and cyclohexyl substituents, but have unchanged number of the O atoms in a cycle. The phenyl and cyclohexyl derivatives of 18-crown-6 are found to be more efficient extractants of alkali metals as compared with unsubstituted crown ethers. However, the selectivity of separation of a pair Cs-Na remains low. The 18-crown-6 derivatives with one and two cyclohexyl fragments selectively extract Sr, which can be used to separate it from the remaining alkali and alkaline-earth metals. An increase in the size of a macrocycle from 18 to 20 and 22 atoms leads to a reduction in the extraction efficiency for all alkali and alkaline-earth metals, insignificantly improves separation of a pair Cs-Na, but noticeably deteriorates Sr-Na separation.     

Chemical assembly of a new heterometallic trimethylacetate cluster with the Co6Ni2 core

Co-thermolysis of the tetranuclear trimethylacetate clusters M₄(₃-OH)₂(OOCCMe₃)₆(HOEt)₆ (M = Co or Ni; the reagent ratio was 1 : 1) in decalin (2 h, 170 °C) afforded the octanuclear heterometallic cluster Co₆Ni₂(₄-O)₂(₂-OOCCMe₃)₆(₃-OOCCMe₃)₆, which exhibits ferromagnetic properties at 10—8 K.     

Study of isotope effect upon lithium iodide complexation with benzo-15-crown-5 in water–chloroform extraction system

Extraction characteristics of chloroform–water system in lithium iodide extraction with benzo-15-crown-5 (B15C5) were studied. The complexation of the crown ether with LiI in organic phase was shown by IR spectroscopy. Isotope effect multiplication was performed by extraction chromatography technique. The magnitude of isotope separation factor (α) for ⁶Li-⁷Li pair was 1.017. The light lithium isotope is concentrated in organic phase.     

Americium(III) sorption from multicomponent solutions by macrocyclic polyester-based sorbents

Americium sorption by crown-ether-impregnated polymeric sorbents from nitric acid solutions and multicomponent nitrate solutions that model process solutions was studied. Sorption of ballast elements by the unimpregnated Porolas-T support was studied. The sorption coefficients K _d of these elements on Porolas-T do not exceed 0.01. Sorption of the same elements by crown-ether-impregnated sorbents was also studied. Dicyclohexano-18-crown-6 (DCH18C6) and its alkyl derivatives were used. Sorption coefficients were determined for all ballast elements. At the final stage of the study, ²⁴¹Am sorption coefficients of from multi-component solutions were determined. The data obtained signify the utility of crown-ether-impregnated sorbents for recovering ²⁴¹Am from multicomponent technological solutions.     

Tetra-15-Crown-5-Phthalocyaninatocobalt as a Reagent for the Spectrophotometric Determination of Potassium and Sodium in Chloroform–Ethanol–Water Solutions

It is shown that potassium and sodium simultaneously present in aqueous solutions can be determined by photometry with the use of tetra-15-crown-5-phthalocyaninatocobalt.     

Extraction of rare-earth elements by alkylated dibenzo-18-crown-6 and dicyclohexano-18-crown-6 from acid solutions

The extraction of rare-earth elements (REE) by alkylated crown ethers (dibenzo-and dicyclohexano-18-crown 6; DB18C6 and DCH18C6) from acid solutions in the chloroform-water system is studied. The extraction of the REE with DCH18C6 and its alkylated derivatives in the presence of trichloroacetic acid (TCA) is far more efficient than the extraction with DB18C6 and its alkylated derivatives or when nitric or acetic acid is used instead of TCA. The distribution coefficients for the cerium metals are far higher than for the yttrium metals. The metal: crown ether ratio in the extracted complex in all cases is 1:1.     

Unsymmetrical dinuclear cobalt and nickel trimethylacetate complexes

The reaction of the dinuclear complex Co₂(-OOCCMe₃)₂(²-OOCCMe₃)₂bpy₂ (1) with the polymer [Co(OH) _n (OOCCMe₃)_2–n ] _x afforded the unsymmetrical dinuclear complex bpyCo₂(₂-O,²-OOCCMe₃)(₂-O,O"-OOCCMe₃)₂(²-OOCCMe₃) (2). The reaction of 2,2"-dipyridylamine with [Co(OH) _n (OOCCMe₃)_2–n ] _x gave rise to the analogous complex [(C₅H₄N)₂NH]Co₂(₂-O,²-OOCCMe₃)(-OOCCMe₃)₂(²-OOCCMe₃) (3). The reaction of complex 1 with Ni₄(₃-OH)₂(-OOCCMe₃)₄(OOCCMe₃)₂(MeCN)₂[²-o-C₆H₄(NH₂)(NHPh)]₂ (4) produced an isostructural heterometallic analog of complex 2 with composition bpyM₂(₂-O,²-OOCCMe₃)(₂-O,O"-OOCCMe₃)₂(²-OOCCMe₃) (5) (M = Co, Ni; Co : Ni = 1 : 1) and the dinuclear heterometallic complex bpy(HOOCCMe₃)M(-OH₂)(-OOCCMe₃)₂M(OOCCMe₃)₂[o-C₆H₄(NH₂)(NHPh)] (6) (M = Co, Ni; Co : Ni = 0.15 : 1.85). Compounds 2 and 5 exhibit ferromagnetic spin-spin exchange interactions.