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1.
V. G. Torgov R. S. Shul’man T. V. Us E. S. Stoyanov T. M. Korda V. A. Emel’yanov 《Russian Journal of Inorganic Chemistry》2007,52(6):953-959
The synergistic extraction of [RuNO(NO2)4OH]2? by diphenyl(dibutylcarbamoylmethyl)phosphine oxide (L) in the presence of nonprecious metal cations (M2+) is studied; the extraction occurs on the account of the formation of heterometal complexes [RuNO(NO2)4OHMLm] (M = Zn, Cu, Co, Ni) due to the addition of M2+ to ruthenium through the oxygen atoms of the OH and NO2 groups and the bidentate coordination of L to M2+. The extraction constants for Ru/M complexes and MLn(NO3)2 are determined. The variation in the extraction constants with changing M (Co, Zn, Cu > Ni) does not agree with the Irwing-Williams row, unlike the extraction with monodentate PO-containing extractants (Zn > Cu > Co > Ni). The feasibility of ruthenium extraction in the form of Ru/M complexes from complex nitrate-nitrite solutions is demonstrated. 相似文献
2.
G. A. Kostin T. V. US T. M. Korda V. G. Torgov N. V. Kuratieva S. I. Miroshnichenko V. I. Kalchenko 《Journal of inclusion phenomena and macrocyclic chemistry》2010,68(1-2):131-137
The extraction of non-ferrous metal (M2+) nitrates by the calix[4,6]arenes (L), bearing four or six phosphine oxide donor groups at the upper or at the lower rim, was quantitatively described in the form of [Mn(NO3)2nL] (n = 1, 2) complexes. The extraction constants (Zn2+ > Cu2+ > Co2+ > Ni2+) for the both types of L coincide with Irving-Williams sequence. Calix[4]arenes, phosphorylated at the lower (narrow) rim, provide better stability of ML complexes because of the best spatial fitting of M2+ by the donor groups. For the upper (wide) rim phosphorylated calix[4]arenes M2L and ML2 complexes are more stable. Unusual zwitterionic [Co2(NO3)4L] complex of the lower rim tetraphosphorylated calix[4]arene 1 was determined by X-ray structural analysis. 相似文献
3.
The reduction of allenyl(diphenyl)phosphine oxides with HSiCl3 or LiAlH4 selectively afforded the corresponding allyl(diphenyl)phosphine oxides. 3-Methylbut-2-en-1-yl(diphenyl)phosphine oxide reacted with AlCl3 to give a mixture of 4,4-dimethyl-1-phenyl-1,2,3,4-tetrahydro-λ5-phosphinoline 1-oxide and 4,4-dimethyl-1-phenyl-1,4-dihydro-λ5-phosphinoline 1-oxide. 相似文献
4.
Dr. Lei Xu Yuxun Hao Xiao Yang Dr. Zhipeng Wang Prof. Chao Xu Prof. Nataliya E. Borisova Mingze Sun Prof. Xingwang Zhang Prof. Lecheng Lei Prof. Chengliang Xiao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(41):10717-10730
Two new phosphine oxide-functionalized 1,10-phenanthroline ligands, tetradentate 2,9-bis(butylphenylphosphine oxide)-1,10-phenanthroline (BuPh-BPPhen, L1 ) and tridentate 2-(butylphenylphosphine oxide)-1,10-phenanthroline (BuPh-MPPhen, L2 ), were synthesized and studied comparatively for their coordination with trivalent actinides and lanthanides. The complexation mechanisms of these two ligands toward trivalent f-block elements were thoroughly elucidated by NMR spectroscopy, UV/vis spectrophotometry, fluorescence spectrometry, single-crystal X-ray diffraction, solvent extraction, and theoretical calculation methods. NMR titration results demonstrated that 1 : 1 and 1 : 2 (metal to ligand) lanthanides complexes formed for L1 , whereas 1 : 1, 1 : 2 and 1 : 3 lanthanide complexes formed for L2 in methanol. The formation of these species was validated by fluorescence spectrometry, and the corresponding stability constants for the complexes of NdIII with L1 and L2 were determined by using UV/vis spectrophotometry. Structures of the 10-coordinated 1 : 1-type complexes of Eu L1 (NO3)3 and [Eu L2 (NO3)3(H2O)] Et2O in the solid state were characterized by X-ray crystallography. In solvent-extraction experiments, L1 exhibited extremely strong extraction ability for both AmIII and EuIII, whereas L2 showed nearly no extraction toward AmIII or EuIII due to its high hydrophilicity. Finally, the structures and bonding natures of the complex species formed between AmIII/EuIII and L1/L2 were analyzed in DFT calculations. 相似文献
5.
Manpreet Singh Arijit Sengupta Sk. Jayabun Tejaswi Ippili 《Journal of Radioanalytical and Nuclear Chemistry》2017,311(1):195-208
The extraction efficiency for thorium followed the trend: Cyanex-923 > Cyanex-272 > DHOA > TBP. In case of TBP and DHOA the extraction proceeded via ‘solvation mechanism’ through Th(NO3)4·2L, while for Cyanex-923 and Cyanex-272 it proceeded via ‘ion exchange’ mechanism through (Th(NO3)2·2L)2+. The extraction process followed slower kinetics while change in Gibb’s energy revealed the spontaneity of the process. These ionic liquid based systems were found to be radiolytically stable, highly efficient and selective for Th. Oxalic acid was found to be suitable for almost quantitative stripping of Th from extracted ionic liquid phase. 相似文献
6.
V. G. Torgov V. V. Us T. M. Korda G. A. Kostin V. I. Kal’chenko 《Russian Journal of Inorganic Chemistry》2011,56(3):473-478
Compared were dialkylcalix[4]phosphine oxides (L) having PO groups in the opposing rims as regards the extraction of [RuNO(NO2)4(OH)]2−, nonprecious metals (M2+), and Ru/M heterometallic complexes of their base. The extraction constants for the ion association {(Na+)2(LH2O)
r
[RuNO(NO2)4(OH)]2− and the degree of aggregation of L were calculated. The destruction of (LH2O)
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
(NO3)2m
] and mononuclear Ru/M species [RuNO(NO2)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 ML2. 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. 相似文献
7.
M. S. Murali K. M. Michael U. Jambunathan J. N. Mathur 《Journal of Radioanalytical and Nuclear Chemistry》2002,251(3):387-391
Extraction, loading and stripping studies of Pu(IV) have been carried out using three phosphine oxides namely CyanexÒ-923 (cyn-923), CyanexÒ-925 (cyn-925) and TOPO in dodecane from nitric acid medium. All the three phosphine oxides have shown very high extraction of Pu. The order of extraction for Pu by these compounds is cyn-923 > TOPO - cyn-925. Loading of Pu (30.0 mg/l) in 3.0M HNO3 was carried out using 5% solution of each of the phosphine oxides in dodecane. It was found that even at an organic to aqueous phase ratio of 1:10, the loading of Pu is >96%. From the loaded organic phase, Pu could be almost quantitatively stripped using 0.1 or 0.5M oxalic acid. The extraction of Pu(IV) with cyn-925 has also been carried out from HCl, HNO3 or HClO4 (0.5 to 9.1M). The species extracted into the cyn-925/dodecane phase from 3.0M HNO3 or HCl media was found to be Pu(L)4
.2 cyn-925 where L = NO3
– or Cl–. Similar species were observed to be formed when dodecane was replaced by xylene, chlorobenzene or o-dichlorobenzene. 相似文献
8.
P. Benzi F. Nebbóa R. Righetti P. Volpe 《Journal of Radioanalytical and Nuclear Chemistry》1995,191(1):15-24
The determination of carbon, hydrogen, nitrogen, fluorine, chlorine and sulphur contents for characterization of plutonium complexes with organic ligands have been standardized and glove box adopted. Various plutonium(IV) mono- and di-carboxylates, plutonium(IV) chelates with pyrazolones, UO
2
++
and PuO
2
++
complexes having pyrazolones as chelating agent and sulfoxides, amides and phosphine oxide ligands as oxodonors; uranium carbides and uranium nitrides and several potential organic extractants for actinides were analyzed satisfactorily. All these methods set up in double module glove box train are extremely useful for a low budget radioactive laboratory engaged in research in solid actinide complexes. 相似文献
9.
The fluorohydroxylation of allenyl phosphine oxides with Selectfluor in commercial MeCN without prior treatment or a mixed solvent of anhydrous MeCN (refluxed over CaH2 and distilled before use) and 7.0 equiv of H2O or MeNO2/H2O=10/1 afforded 2-fluoro-3-hydroxy-1(E)-alkenyl diphenyl phosphine oxides in moderate yields with very high regio- and stereoselectivities. The E-stereoselectivity is believed to be controlled by the phosphine oxide functionality. In the reaction of 3-(4-methoxyphenyl)-1,2-propadienyl diphenyl phosphine oxide, further fluorination on the electron-rich phenyl ring was also observed. 相似文献
10.
The selenohydroxylation of readily available 1,2-allenyl phosphine oxides with PhSeCl in MeCN/H2O afforded 3-hydroxy-2-phenylselanyl-1(E)-alkenyl diphenyl phosphine oxides in good yields with very high regio- and stereoselectivities including the high efficiency of the axial chirality transfer. The E-stereoselectivity is believed to be determined by the neighboring group participation effect of the diphenyl phosphine oxide functionality. 相似文献
11.
Daniel Lee Magorzata Wolska‐Pietkiewicz Saumya Badoni Agnieszka Grala Janusz Lewiski Gaël De Paëpe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(48):17323-17328
The unambiguous characterization of the coordination chemistry of nanocrystal surfaces produced by wet‐chemical synthesis presently remains highly challenging. Here, zinc oxide nanocrystals (ZnO NCs) coated by monoanionic diphenyl phosphate (DPP) ligands were derived by a sol‐gel process and a one‐pot self‐supporting organometallic (OSSOM) procedure. Atomic‐scale characterization through dynamic nuclear polarization (DNP‐)enhanced solid‐state NMR (ssNMR) spectroscopy has notably enabled resolving their vastly different surface‐ligand interfaces. For the OSSOM‐derived NCs, DPP moieties form stable and strongly‐anchored μ2‐ and μ3‐bridging‐ligand pairs that are resistant to competitive ligand exchange. The sol‐gel‐derived NCs contain a wide variety of coordination modes of DPP ligands and a ligand exchange process takes place between DPP and glycerol molecules. This highlights the power of DNP‐enhanced ssNMR for detailed NC surface analysis and of the OSSOM approach for the preparation of ZnO NCs. 相似文献
12.
Christos G. Nanos Miltiades I. Karayannis 《Fresenius' Journal of Analytical Chemistry》1991,340(4):253-257
Summary A simple, rapid and non-destructive method for the detection and determination of phosphines and phosphine oxides in solution by 1H and 31P NMR spectroscopy is proposed. Diphenylphosphine (DPP) and diphenylphosphine oxide (DPPO) mixtures in C6D6 chosen as model system were studied in wide ranges of concentration (10–2 to 4 mol/l). The detection of DPP and DPPO in solution by 1H NMR was based on the presence of two doublets (hydrogen directly bonded to phosphorus, HP) originating from P-H and P(O)H groups with one bond coupling constant 1JPH of 216.08 and 476.12 Hz. 31P NMR signals at –40.07 and +18.26 ppm additionally proved the presence of DPP and DPPO in solution. A linear dependence of the measured HP and ortho-proton integral intensity on the concentration of DPP and DPPO was found. The content of DPP and DPPO evaluated by 31P without adding Cr(acac)3 and by 1H NMR agreed with the quoted amounts within 1 to 3%.Under Indo-Polish cultural exchange programme, temporarily at Silesian University 相似文献
13.
The preparation, spectroscopic characterization and thermal stability of neutral complexes of uranyl ion, UO2
2+, with phosphonate ligands, such as diphenylphosphonic acid (DPhP), diphenyl phosphate (DPhPO) and phenylphosphonic acid (PhP)
are described. The complexes were prepared by a reaction of hydrated uranyl nitrate with appropriate ligands in methanolic
solution. The ligands studied and their uranyl complexes were characterized using thermogravimetric and elemental analyses,
ESI-MS, IR and UV–Vis absorption and luminescence spectroscopy as well as luminescence lifetime measurements. Compositions
of the products obtained dependent on the ligands used: DPhP and DPhPO form UO2L2 type of complexes, whereas PhP forms UO2L complex. Based on TG and DTG curves a thermal stability of the complexes was determined. The complexes UO2PhP·2H2O and UO2(DPhPO)2 undergo one-step decomposition, while UO2PhP · 2H2O is decomposed in a two-step process. The thermal stability of anhydrous uranyl complexes increases in the series: DPhPO < PhP < DPhP.
Obtained IR spectra indicate bonding of P–OH groups with uranyl ion. The main fluorescence emission bands and the lifetimes
of these complexes were determined. The complex of DPhP shows a green uranyl luminescence, while the uranyl emission of the
UO2PhP and UO2(DPhPO)2 complexes is considerably weaker. 相似文献
14.
Huilu Wu Ying Bai Xiaoli Wang Yanhui Zhang Furong Shi Yuchen Bai Guolong Pan Jin Kong 《Transition Metal Chemistry》2013,38(5):553-561
Tris[2-(N-ethyl)benzimidazylmethyl]amine (Etntb) and two of its complexes, [Zn(Etntb)(cinnamate)]NO3·2DMF (1) and [Ni(Etntb)(cinnamate)·(H2O)]NO3 (2) have been synthesized and characterized by physico-chemical and spectroscopic methods. Single-crystal X-ray diffraction revealed that the complexes have different structures. In complex 1, the coordination sphere around Zn(II) is distorted trigonal bipyramidal, whereas the coordination sphere around Ni(II) is distorted octahedral in complex 2. The DNA-binding properties of the free ligand and its complexes have been investigated by electronic absorption, fluorescence, and viscosity measurements. The results suggest that the ligand and both complexes bind to DNA via an intercalative mode, and their binding affinity for DNA follows the order 1 > 2> ligand. 相似文献
15.
E. G. Il’in A. S. Parshakov V. I. Privalov V. V. Danilov G. V. Bodrin E. I. Goryunov E. E. Nifant’ev 《Doklady Chemistry》2016,467(2):122-125
The composition and structure of the products of the reaction of titanium tetrafluoride with Ph2P(O)(CH2)2C(O)NМе2 (L), the simplest representative of diphenyl[2-(N,N-dialkylcarbamoyl)ethyl]phosphine oxides, in a СН2Сl2 have been studied by 19F and 31P NMR. It has been shown for the first time that functionalized phosphine oxides form stable seven-membered chelate heterocycles on complexes of d° transition metals. On the basis of NMR data, previously unknown conformational isomerism of the seven-membered TiOPCCCO heterocycle in solution has been proposed. A simple and rather efficient method of synthesis of the ligand (L) from commercially available reagents has been developed. 相似文献
16.
M. Montazerozohori 《Journal of Thermal Analysis and Calorimetry》2013,111(1):121-128
Some new coordination compounds of cadmium(II) and mercury(II) with N,N-bis[(E)-3-(phenylprop)-2-enylidene]propanediamine (L) as a new bidentate Schiff base ligand with general formula MLX2 (X = Cl?, Br?, I?, SCN?, and N3 ?) have been prepared. They were characterized by elemental analysis, FT-infrared (FT-IR) and Ultraviolet–Visible spectra, 1H- and 13C-NMR spectra. The reasonable shifts of FT-IR and NMR spectral signals of the complexes with respect to the free ligand confirm well coordination of ligand and anions(X-) in inner sphere coordination mode. The thermal behavior of the complexes from room temperature to 800 °C shows weight loss by decomposition of the anions and ligand segments in the subsequent steps. The results showed that cadmium complexes have no water molecules (neither as lattice nor as coordinated water) and are decomposed in two temperature steps except about cadmium thiocyanate complex that is decomposed in three steps. Final residual contents of cadmium complexes are suggested to be cadmium oxide or sulfide. Mercury complexes were decomposed in three to four temperature steps. Mercury bromide and azide complexes leave out a little amount of mercury oxide in final, while mercury chloride, iodide, and thiocyanate complexes were found to be completely decomposed without any residual matter. 相似文献
17.
Igor Yu. Kudryavtsev Tat’yana V. Baulina Margarita P. Pasechnik Sergei V. Matveev Anna G. Matveeva 《Phosphorus, sulfur, and silicon and the related elements》2014,189(7-8):946-962
AbstractA new tripodal O-donor ligand, tris(2-N,N-dibutylcarbamoylmethoxyphenyl)phosphine oxide (L), was synthesized. This potentially tetradentate ligand L exhibits variable denticity upon complexation with UO2(NO3)2, Nd(NO3)3, and Lu(NO3)3. The complexes were studied by elemental analysis, IR, and 1H, 13C, and 31P NMR spectroscopy.[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional text, tables, and figures.] 相似文献
18.
V. G. Torgov T. V. Us R. S. Shul’man T. M. Korda G. A. Kostin V. I. Kal’chenko 《Russian Journal of Inorganic Chemistry》2008,53(11):1816-1826
Synergetic extraction of [RuNO(NO2)4OH]2? by calix[4]arene phosphine oxides (L) in the form of Ru/M heterometallic complexes was studied in the presence of nonprecious metals (M2+). The main extraction laws were recognized for [M(NO3)2L n ] and [RuNO(NO2)4OH])ML m ], where M2+ = Zn2+, Cu2+, Co2+, or Ni2+ and n, m = 1 or 2; extraction constants were determined for these metals. The variation row of the extraction constants with varying metal (Zn2+ > Cu2+ > Co2+ > Ni2+) coincides with the Irving-Williams row. Two or three PO groups of extractant L and the OH and NO2 groups of the ruthenium anion are coordinated to the M2+ atom in Ru/M complexes. The conditions for generation of the Ru/Zn complex and its complete extraction were optimized as applied to the extraction of fission ruthenium from nitrated nitric acid and imitation solutions. 相似文献
19.
Ya. A. Vereshchagina A. Z. Alimova D. V. Chachkov E. A. Ishmaeva O. I. Artyushin E. V. Sharova A. E. Klimovitskii R. R. Khanafieva 《Russian Journal of Organic Chemistry》2014,50(6):796-799
The polarity and conformations of 2-aminophenyl-, 2-aminobenzyl-, and 2-nitrobenzyl(diphenyl)-phosphine oxides were studied by the dipole moment method, IR spectroscopy, and quantum chemical calculations. 2-Aminophenyl- and 2-aminobenzyl(diphenyl)phosphine oxides were found to exist preferentially as conformers with intramolecular hydrogen bond. 2-Nitrobenzyl(diphenyl)phosphine oxide is likely to be represented by equilibrium mixture of three conformers in which the phosphoryl and nitro groups are oriented syn or anti with respect to the \(PC_{sp^3 } C_{sp^2 } \) fragment. 相似文献
20.
《Tetrahedron》2007,63(22):4748-4755
Starting from p-adamantylcalix[4]- and [6]arenes functionalized with carboxylic acid or ester groups at the adamantane nuclei, carbamoylmethylphosphine oxide (CMPO)-containing ligands of a novel type were synthesized. They were studied as extractants for a series of f-block elements including radioactive 152Eu(III), 241Am(III), 233U(VI), and 239Pu(IV). Tetrameric ligand 4b in which CMPO residues are connected to adamantane nuclei through methylene groups gave the best extraction results for lanthanides and actinides. For all the ligands the extraction efficiency does not decrease at higher nitric acid concentration. Although the discrimination between trivalent actinides and lanthanides is not good, all ligands are highly selective for thorium(IV) with the best separation factor achieved in the case of hexameric ligand 5 (DTh/DLn>24). 相似文献