A novel CMPO-functionalized task specific ionic liquid ... novel CMPO-functionalized task specific ionic liquid: Synthesis, extraction and spectroscopic investigations of actinide
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A novel CMPO-functionalized task specific ionic liquid:
Synthesis, extraction and spectroscopic investigations of
actinide and lanthanide complexes
Prasanta K. Mohapatra, Pankaj Kandwal, Mudassir Iqbal,
Jurriaan Huskens, Mallekav S. Murali, and Willem Verboom
Radiotracers 241Am, Pu (mainly 239Pu), and 233U tracers from laboratory stock solutions were purified
prior to their use by ion-exchange methods reported previously. 85,89Sr and 137Cs and 152,154Eu tracers were purchased from BRIT, Mumbai. Assaying of 241Am, 137Cs, 85,89Sr
and 152,154Eu was done by gamma counting using a NaI(Tl) scintillation counter (Para
Electronics, India) interphased to a multi-channel analyzer (ECIL, India), while nuclides
such as 239Pu and 233U were assayed by liquid scintillation counting (Hidex, Finland)
using a toluene-based scintillator cocktail (Sisco Research Laboratory, Mumbai) to
minimize quenching effects.
Reagents
CMPO (n-octylpheyl-N,N-di-iso-butylcarbamoylmethylphosphine oxide) was procured
from Orion Chemicals, Mumbai and was passed through a basic alumina column prior to
use. AR grade n-dodecane was obtained from Lancaster, UK, and was used as such.
Suprapur nitric acid (Merck, Germany) was used for preparing nitric acid solutions using
milliQ water (Millipore, India). For spectrophotometric studies, the uranyl nitrate (UED,
BARC) and neodymium nitrate (Aldrich, USA) salts were used, which were standardized
using a normal procedure.24 All the other reagents were of AR grade.
Synthesis of TSILs
All reactions were carried out under an argon atmosphere. The solvents and all reagents
were obtained from commercial sources and used without further purification. Solvents
were dried according to standard procedures and stored over molecular sieves. 1H NMR
and 13C NMR spectra were recorded on a Varian Unity INOVA (300 MHz) spectrometer. 1H NMR (300 MHz) and 13C NMR (75 MHz) chemical shift values are reported as δ
using the residual solvent signal as an internal standard. All NMR measurements are
recorded in CDCl3 as a solvent. Electrospray Ionization (positive mode) high resolution
mass spectra were recorded on a WATERS LCT mass spectrometer. Analytical TLC was
performed using Merck prepared plates (silica gel 60 F-254 on aluminum).
1-(3-(2-(Diphenylphosphoryl)acetamido)propyl)-3-dodecyl-1H-imidazol-3-ium bromide (2). To a solution of CMPO-imidazole-propanamide (Ref: I. L. Odinets, E. V. Sharova, O. I.
Artyshin, K. A. Lyssenko, Y. V. Nelyubina, G. V. Myasoedova, N. P. Molochnikova, E.
A. Zakharchenro, Dalton Trans., 2010, 39, 4170-4178) 1 (26.00 g, 70.8 mmol) in CH3CN
(150 mL), n-dodecyl bromide (21.2 g, 85.0 mmol) was added dropwise at 0 °C. The
mixture was stirred at room temperature for 12 h, followed by reflux at 80–85 °C for 2.5
d. Then the solvent was evaporated under reduced pressure and the resulting residue was
washed with n-hexane (3 × 100 mL). Residual solvent was removed under reduced
pressure and the residue was dried under vacuum for 5 h to afford 2 (37.9 g, 87%) as a
Fig. S-2 Variation of DAm with ligand concentration; (a) CMPO-TSIL L-II as ligand and (b) CMPO as ligand. [Ligand]: 0.1 M in ionic liquid; Aqueous phase: 3 M HNO3
0.01 0.1
0.01
0.1
1
10
100
D Am
[TSIL], M
TSIL in C4mimNTf2 TSIL in C6mimNTf2 TSIL in C8mimNTf2 Regression lines
(a)
0.01 0.1
1
10
100
D Am
[CMPO], M
CMPO in C4mimNTf2 CMPO in C6mimNTf2 CMPO in C8mimNTf2 Regression lines
IR Spectral study The IR spectra of the following samples are enclosed at the end of the ESI. S.No. Sample name Details 1. PK3 Uranyl nitrate extract using 0.1 M CMPO in C8mimNTf2 2. PK4 0.1 M CMPO in C8mimNTf2 3. PK6 0.1 M TSIL in C8mimNTf2