共查询到20条相似文献,搜索用时 31 毫秒
1.
A. G. Matveeva A. M. Thu A. M. Safiulina G. V. Bodrin E. I. Goryunov I. B. Goryunova O. A. Sinegribova E. E. Nifant’ev 《Russian Chemical Bulletin》2013,62(6):1309-1316
The extraction ability and selectivity of a series of phosphoryl ketones Ph2P(O)CH2C(O)Me, and Ph2P(O)CRR’CH2C(O)Me (R = H, Me; R’ = H, Me, n-C5H11, Ph, 2-thienyl, 2-furyl) towards trivalent lanthanides (LaIII, NdIII, HoIII, YbIII) and actinides (UVI, ThIV) were studied. The efficiency and selectivity of the new ligands in the extraction of f-elements from nitric acid solutions into chloroform were compared to those of model phosphine oxide Ph2P(O)Bu and known extractants: tributyl phosphate (BuO)3P(O), trioctylphosphine oxide (C8H17)3P(O), and carbamoylmethyl phosphine oxide Ph2P(O)CH2C(O)NBu2. 相似文献
2.
Shyamapada Shit Soma Sen Samiran Mitra David L. Hughes 《Transition Metal Chemistry》2009,34(3):269-274
Two new square-planar Ni(II) complexes, [NiL1(NCS)] (1) and [NiL2(N3)] (2) have been synthesized with the unsymmetrical tridentate Schiff base ligands [(CH3)2NCH2CH2N=C(CH3)CH=C(OH)(C6H5)], L
1
H, derived from benzoylacetone and 2-dimethylaminoethylamine and [(CH3CH2)2NCH2CH2N=C(CH3)CH=C(OH)(C6H5)], L
2
H, derived from benzoylacetone and 2-diethylaminoethylamine, respectively. The complexes have been characterized by elemental
analysis, FT-IR, UV-Vis spectroscopy, electrochemical and thermal methods (where applicable). Structures have been established
by the single-crystal X-ray diffraction technique which reveals the discrete nature of the complexes in which the metal centers
adopt a distorted square planar geometry. Coordination environments of the metal ions in the complexes are satisfied with
two different unsymmetrical Schiff base ligands having similar N2O donor sets and a terminal pseudohalide anion (thiocyanate for 1 and azide for 2). 相似文献
3.
《Journal of Coordination Chemistry》2012,65(9):1476-1483
Two isostructural dinuclear lanthanide(III)/Schiff-base complexes [{Ce1.5Eu0.5(clapi)}2]·2CH3CN (1) and [{La1.5Eu0.5(clapi)}2]·2CH3CN (2) {H3clapi = 2-(5-chloride-2-hydroxyphenyl)-1,3-bis[4-(5-chloride-2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine} have been prepared by template procedure and characterized by elemental analyses, ICP, IR, and single-crystal X-ray diffraction analyses. Lanthanide ions Ce(III) and Eu(III) in 1, and La(III) and Eu(III) in 2 are disordered with occupancies 0.75 for Ce and 0.25 for Eu in 1; 0.75 for La and 0.25 for Eu in 2. In the compounds, each lanthanide is coordinated to four N and four O atoms from two clapi3? ligands, forming a distorted square antiprism. Two phenol oxygen atoms from the middle arms of the two heptadentate μ2-bridging ligands connect the two Ce(Eu) atoms in 1, and La(Eu) in 2. The solution of the two complexes in CH2Cl2 exhibits red fluorescence from Eu3+ ions at 77 K, very weak at room temperature. 相似文献
4.
On the Reaction of Phosphorous Acid Esters with Nucleophiles in the Presence of Carbon Tetrachloride
Lothar Riesel Eckhard Herrmann Jörg Steinbach 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-3):253-256
Abstract Esters of N-Phosphoryl phosphazenes are prepared by a modified Atherton-Todd reaction from di- and triesters of phosphorous acid, sodium azide, and carbon tetrachloride in high yields. The utilization of the two-component system trialkyl phosphite/ carbon tetrachloride for preparing phosphazenes, (RO)3P[dbnd]NY (Y: PO(OR)2, SO2R, COR, CN), and dialkoxyphosphoryl compounds, (RO)2P(O)X (X: NHR, NR2, OPh, CN, F, NCO), is presented. 相似文献
5.
A. N. Turanov V. K. Karandashev E. V. Sharova O. I. Artyushin I. L. Odinets 《Russian Journal of Inorganic Chemistry》2011,56(3):467-472
The extraction of trace amounts of scandium(III) from HCl,HNO3, and HClO4 solutions in the form of complexes with neutral polyfunctional organophosphorus compounds bis(diphenylphosphorylmethylcarbamoyl)alkanes
[Ph2P(O)CH2C(O)NH]2(CH2)
n
(n = 3, 5, 8) was studied. The effect of the structure of the extractant, the aqueous phase composition, and the nature of the
organic solvent on the efficiency of transition of scandium(III) ions into the organic phase was considered, and the stoichiometry
of the extracted complexes was determined. The studied ligands exhibit a higher extraction power toward scandium(III) ions
than their analog Ph2P(O)CH2C(O)NHC9H19 containing only one bidentate carbamoylmethylphosphoryl moiety per molecule. Scandium(III) passes into the organic phase
most efficiently in the presence of HClO4 in the aqueous phase. It was shown that scandium(III) can be selectively recovered
and preconcentrated by a complexing adsorbent obtained by noncovalent immobilization of bis(diphenylphosphorylmethylcarbamoyl)pentane
on a macroporous polymer matrix. 相似文献
6.
A. M. Safiulina A. G. Matveeva T. K. Dvoryanchikova O. A. Sinegribova A. M. Tu D. A. Tatarinov A. A. Kostin V. F. Mironov I. G. Tananaev 《Russian Chemical Bulletin》2012,61(2):392-398
Extraction capability and selectivity of acetyl-containing phosphine oxides R2P(O)CMe2CH2C(O)Me (R = Pr, Bu, n-C5H11, n-C6H13, n-C8H17, Ph) toward actinides (UVI, ThIV) and trivalent lanthanides (LaIII, NdIII, HoIII, YbIII) were studied. The new ligands were shown to be more efficient and selective in the extraction of uranium, thorium, and heavy lanthanides from nitric acid solutions into chloroform as compared to the known extractants such as carbamoylphosphine oxide Ph2P(O)CH2C(O)NBu2, trioctylphosphine oxide (n-C8H17)3P(O), and tributyl phosphate (n-BuO)3P(O). 相似文献
7.
Ludwig Maier 《Helvetica chimica acta》1969,52(3):827-845
High yields of bis-(dialkoxyphosphonyl-methyl)- phosphinic esters, (RO)2 (O)-PCH2P(O)OR, bis-(aloxyphosphinyl-methyl)-phosphinic esters, [R(RO)(O)PCH2]2P(O)OR, are obtained by heating bis-chloromethyl-phosphinic esters, (CICH2)2P(O)OR, with alkylphoshites, phosphonites and phosphinites, repectively, at 170 to 180°C for several hours. Hydrolysis of these esters in achieved by refluxing with conc. HCl for extended periods. Bis-(dihydroxyphosphonyl-methyl)-phosphinic acid, HO(O)P[CH2P(O) (OH)2]2, obtained by hydrolysis of the all-ethyl ester, titrates in aqueous solution as a tetrabasic acid with breaks at pH = 5,2 (three equivalents) and at pH = 8,8 (one equivalent). The fifth proton can be titrated only after addition of NaCl. This acid is an excellent chelating agent for metal ions. The 1H- and 31P-NMR. spectra of all the compounds prepared are discussed. 相似文献
8.
E. I. Matrosov A. G. Matveeva N. P. Nesterova M. I. Tere-khova E. S. Petrov M. I. Kabachnik 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Carbamoylmethylphosphoryl compounds (CMP) are used as neutral bifunctional extractants. However, little is known about acid-base properties of these compounds. We have studied CH-acidity and basicity of selected CMP, RR′P(O)CH2C(O)NEt2 with R,R′ = Alk, Alk2N, Ar, AlkO, and also H-complexes of CMP with HNO3. 相似文献
9.
Bis(trimethylsilyl)hypophosphite und Alkoxycarbonylphosphonous Acid Bis(trimethylsilyl) esters as Building Blocks in Organophosphorus Chemistry The oxidation of pure bis(trimethylsilyl)hypophosphite ( BTH ) with chalcogenides forming (Me3SiO)2P(X)H (X = O, S, Se, Te) is described as well as its reactions with alkylhalides RX (X = Cl, Br, I) and Cl? C(O)OR (R = Me, Et, Bzl). By reaction with oxygen, sulfur, and selenium the alkoxycarbonylphosphonous acid bis(trimethylsilyl)esters form RO? C(O)? P(X)(OSiMe3)2 (X = O, S, Se) whereas with Cl? C(O)OR the bis(alkoxycarbonyl)-phosphinic acid trimethylsilylesters are obtained. After partial hydrolysis the resulting instable RO? C(O)? P(O)H(OSiMe3) gives RO? C(O)? P(O)(OSiMe3)? CH2? NH? A? COOR′ (A = CH2, CH2CH2, CHCH3, CH2CH2SH, CHCH(CH3)2,…) when allowed to react with hexahydro-s-triazines of the aminoacid esters. Reactions of the alkoxycarbonyl-P-silylesters with NaOR or NaOH result in the corresponding mono-, di-, or trisodium salts. With mineral acids decarboxylation occurs, but H? P(O)(OH)? CH2? NH? A? COOH can be obtained, too. The structure of the compounds described are discussed by their n.m.r. data. 相似文献
10.
水热条件下合成了具有超大孔道和层状结构的有机模板稀土硫酸盐。超大孔道的稀土硫酸盐(1)的分子式为[(CH3)2NH2]9[Pr5(SO4)12]·2H2O,它展现出有趣的交叉二十元环孔道结构。层状的稀土硫酸盐的分子式为[H3O]3[(CH3)2NH2]3[Ln2(SO4)6](Ln=Pr,2;Nd,3),它可以被看作是由双链和八元环结合而成。这3种化合物的合成揭示了大的有机胺(三聚氰胺)可能用作为第二结构导向剂,阻止形成高维数的无机骨架,从而诱导了二维层状结构稀土硫酸盐晶体的生长。对化合物1和3的磁性进行了研究,测试的温度范围在2~300 K。 相似文献
11.
Jing-Lin Zhang Xiao-Bo Ma 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):15-20
Abstract The title reaction was investigated to find that only substitution reaction on amino group occurred when (2-benzothiazolyl)sulfenamides 1 reacted with P(NR2,)3, whereas the treatment of 1 with (RO)P(NR2,)2, gave derivatives of phosphorodiarnidothioic acid together with 2-alkylthiobenzothiazole and its isomer in addition to substitution products, and no substitution products obtained when N-substituted analogues of 1 were treated similarly. 相似文献
12.
Jiu-Nan Lu Pei-Pei Sun Yue-Ying Yuan Qing-Lun Wang 《Journal of Coordination Chemistry》2018,71(9):1430-1441
Three new lanthanide compounds were obtained using 2-(3-methylthiophene)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) (NIT-3Methien). These compounds, [Gd(hfac)3(NIT-3Methien)2]?0.5CH3(CH2)5CH3 (1: Half n-heptane trihexafluoroacetylacetonate-di-2-(3-methylthiophene)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide gadolinium(III)), [Tb(hfac)3(NIT-3Methien)2]?0.5H2O (2: Half Hydrate trihexafluoroacetylacetonate-di-2-(3-methylthiophene)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide terbium(III)), and [Dy(hfac)3(NIT-3Methien)2]?0.5H2O (3: Half Hydrate trihexafluoroacetylacetonate-di-2-(3-methylthiophene)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide dysprosium(III)), (CH3(CH2)5CH3 = n-heptane), (hfac = hexafluoroacetylacetonate), were characterized structurally and magnetically. The three compounds crystallize in the triclinic space group P1( - ). Ln(III) ion was eight-coordinate by six oxygens from three hfac ligands and two oxygens from two radicals. In 1, direct current (DC) magnetic studies reveal ferromagnetic interactions between the Gd(III) ion and radicals with J1 = 0.94 cm?1. In 2 and 3, there are antiferromagnetic interactions between the Tb(III), or Dy(III) ions and radicals. The luminescence characterizations show that 2 exhibits highly selective luminescent sensing of Cr2O72? ions. 相似文献
13.
Die Reaktion der Zweikomponentensysteme P(OR)3 − x(NR2)x (x = 0–3)/CCl4 und P4/CCl4 mit HF-Donatoren
Reaction of the Two-component Systems P(OR)3 ? x(NR2)x (x = 0–3)/CCl4 and P4/CCl4 with HF-Donators The combination of organylammonium fluorides and carbon tetrachloride is a good agent for oxidative fluorination of trivalent phosphorus compounds. As oxidation products [(RO)PF5]? and (RO)2P(O)F are obtained from P(OR)3, (Et2N)2P(O)F and (Et2N)2(EtO)PF2 from P(OEt)(NEt2)2 as well as (Et2N)3PF2 and [(Et2N)3PF]+ from P(NEt2)3. In the system R2NH/CCl4/Et3N · n HF P4 is fast oxidized forming [HPF5]?, R2NH · PF5 and (R2N)2P(O)F. In the case of simultaneous addition of alcohols [(RO)PF5]?, (RO)3PO and (R2N)2P(O)F are formed. The reactions are controlled by the nucleophilic power and the concentration of fluoride, the acidity of the system, and the temperature. 相似文献
14.
制备了以3-((4,6-二甲基-2-嘧啶基)硫代)-丙酸(HL)和菲咯啉(Phen)为配体的2个三元稀土配合物[Eu(L)3(Phen)]2·2H2O(1)和[Tb(L)3(Phen)]2·2H2O(2),并对其结构进行了表征。单晶X射线衍射分析表明它们是同构的。2个稀土离子(Ln)由4个羧酸配体桥接,形成二聚体排列。其余2个羧酸配体和Phen以双齿螯合方式与Ln配位。Ln的配位数为9,具有扭曲的单端方形反棱柱配位多面体构型。固态光致发光测试表明,这2种配合物都显示了金属中心的特征发射带。 相似文献
15.
水热条件下合成了具有超大孔道和层状结构的有机模板稀土硫酸盐。超大孔道的稀土硫酸盐(1)的分子式为[(CH3)2NH2]9[Pr5(SO4)12]·2H2O,它展现出有趣的交叉二十元环孔道结构。层状的稀土硫酸盐的分子式为[H3O]3[(CH3)2NH2]3[Ln2(SO4)6](Ln=Pr,2;Nd,3),它可以被看作是由双链和八元环结合而成。这3种化合物的合成揭示了大的有机胺(三聚氰胺)可能用作为第二结构导向剂,阻止形成高维数的无机骨架,从而诱导了二维层状结构稀土硫酸盐晶体的生长。对化合物1和3的磁性进行了研究,测试的温度范围在2~300 K。 相似文献
16.
Baoming Ji Dongsheng Deng Zhiqiang Wang Xianming Liu Shaobin Miao 《Structural chemistry》2008,19(4):619-623
Two supramolecular complexes Ni[(Py)2C(OH)2]2·(CH3COO)2·4H2O 1 and Co[(Py)2C(OH)2]2·(CH3COO)2·2H2O 2 have been synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR spectra, and
X-ray single-crystal diffraction. The X-ray diffraction analysis indicates that the center metal (Ni2+ and Co2+) ions having the same coordination environments are chelated by two pyridyl N atoms and a hydroxyl O atom of the gem-diol ligand in an octahedral geometry. In 1, the lattice water molecules form infinite single helical chains, while in 2, two lattice water molecules are discrete. In their crystal structures, intermolecular O–H···O and C–H···O hydrogen bonds
form an extensive three-dimensional network, which consolidates the crystal packing. 相似文献
17.
《Journal of Coordination Chemistry》2012,65(24):3973-3980
Two lanthanide coordination polymers, [Ln2(dpdc)3(H2O)2] n (Ln = Sm 1, Dy 2; dpdc = 2,2′-diphenyldicarboxylate) were prepared by hydrothermal reaction and characterized by elemental analyses, IR spectroscopy, thermogravimetry, fluorescence spectrometry, and single-crystal X-ray diffraction. X-ray studies indicate that the two complexes are isostructural, with two different lanthanide ion nodes linked by dpdc ligands into an infinite one-dimensional chain structure, in which dpdc ligands are bidentate-bridging/bidentate-bridging and bidentate-bridging/chelate-bridging. Complexes 1 and 2 exhibit luminescent characteristics of Sm(III) and Dy(III) ions, respectively. 相似文献
18.
Wolfgang Klui 《Helvetica chimica acta》1977,60(4):1296-1303
Synthesis and NMR. Spectra of Novel Lanthanide-Cobalt Sandwich Compounds The reaction of [(C5H5)Co{P(O)(OR)2}2{P(OH)(OR)2}] ( 3 , R = CH3, C2H5) with lanthanide(III) compounds yields the cationic trinuclear complexes [{(C5H5)Co[P(O)(OR)2]3}2Ln]⊕X? ( 2 , R = CH3, C2H5; Ln = La, Eu, Pr; X = BF4, BPh4). According to thermogravimetric and NMR. studies these compounds do not contain additional coordinated water molecules. It is therefore supposed that the central lanthanide ion has a regular sixfold coordination of phosphoryl ligands. The 31P- and 1H-NMR. spectra of 2 (R = CH3; Ln = La, Eu, Pr) and 3 are discussed. It can be shown that the Fermi contact shift as well as the coordination shift make significant contributions to the observed lanthanide induced shift of the cyclopentadienyl signal.The dominating influence of the Fermi contact interaction on the 31P chemical shift is in accord with theoretical considerations and comparable experimental values. The temperature dependence of the proton chemical shifts of 2 (R = CH3; Ln = Eu) is also discussed. 相似文献
19.
《Journal of Coordination Chemistry》2012,65(9):1547-1559
AbstractCoordination polymers (CPs) of mixed-ligand lanthanide complexes [Ln2(1,3-pdta)(TPA)(H2O)2]n·nH2O [Ln?=?La, 1; Ce, 2; Pr, 3; Nd, 4] (1,3-H4pdta = 1,3-propanediaminetetraacetic acid; H2TPA?= terephthalic acid) were hydrothermally synthesized with flexible 1,3-pdta and rigid TPA ligands. Moreover, lanthanide propanediaminetetraacetates [Ln(1,3-Hpdta)(H2O)]2n·nH2TPA·xH2O [Ln?=?Sm, 5; Gd, 6] with multi-layered structures were also obtained. In 1–4, both 1,3-pdta and TPA coordinate with lanthanide ions through carboxyl oxygen and nitrogen atoms. In 5 and 6, only 1,3-Hpdta coordinates with the central lanthanide ion, where one nitrogen atom in 1,3-Hpdta is protonated, and TPAs are crystallized as H2TPA with the central multi-layered structures of [Ln(1,3-Hpdta)(H2O)]2n through very strong hydrogen bonds [2.504(4) Å]. Solid-state 13C NMR analysis of 1 revealed the coordination of carboxyl groups. However, the methylene groups of 1,3-pdta showed an obvious upfield shift, which can be attributed to the effects of the phenyl ring in TPA ligand. The successful synthesis of these mixed-ligand lanthanides provides a rational design of such lanthanide CPs with flexible and rigid ligands. 相似文献
20.
《Comptes Rendus de l''Academie des Sciences Series IIB Mechanics Physics Astronomy》2000,3(10):757-764
Organophosphorus ligands when grafted onto porous polymers are able to complex with peroxotungstic acid to give immobilised catalytic species for the epoxidation of alkenes with hydrogen peroxide. The macroligands described here contain the phosphoryl (OP) subunit and are related to phosphine oxides R3PO, phosphonic, phosphinic or phosphoric acid amides RP(O)(NRR)2, RR>P(O)NR2 and PO(NR2)3, respectively. These different ligands were introduced in hydrophobic polystyrene and hydrophilic polymethacrylate resins of gel- or macroporous type. This allowed the study of the influence induced on the reactivity and on the selectivity of the epoxidation by the nature of the ligand and by the polar environment around the catalytic sites inside the polymeric beads. 相似文献