The extraction of Mg(II), Ca(II), Sr(II), Ba(II), Mn(II), Co(II), Ni(II), Cu(II), Eu(III) and Am(III) from mineral acid solutions with triethylene glycol bis(dodecyl phosphate) (H2A = HO(H25C12O)P(O)(OCH2CH2)3OP(O)(OC12H25)OH) in different diluents was investigated. The formation of complexes was followed by NMR spectrometry; their composition in the organic phase was determined by slope analysis and proved by MALDI-TOF mass spectrometry. MII(HA)2 and MIII(HA)A species are formed in the organic phase while Mz+(H2m-zAmz-)· nOcOH species (m = 2 or 3; n = 0, 1, 2; z = 2 or 3) in (octan-1-ol)-containing diluents.

The distribution of chelate-forming reagents on a basis of arylimidodiphosphate between different organic solvents and 0.1 mol L−1 HNO3 has been studied by liquid-liquid extraction of 46Sc. The values of dimerization constants K2 in selected solvents, particularly on the chlorine and chlorine-fluorine hydrocarbon basis as well as distribution constants KD(HA) have been determined.

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A series of triethylene glycol bis(alkyl phosphate)s HO(RO)P(O)(OCH2CH2)3OP(O)(OR)OH 4 (R = octyl (4a), 1-methylheptyl (4b), 2-ethylhexyl (4c), nonyl (4d), decyl (4e), dodecyl (4f), hexadecyl (4g), octadecyl (4h)) has been synthesized with the expectation that these compounds could be effective complexing and/or extraction agents for metal cations. The compounds were characterized by 31P NMR, 1H NMR, 13C NMR and IR spectroscopy, MALDI-TOF mass spectroscopy and elemental analysis.

(PhO)(2)P(S)-NH-C (CH3)=CH-CN (PCNS) and (PhO)(2)P(O)-NH-C(CH3)=CH-CN (PCNO) are formed by the reaction of acetonitrile with (PhO)(2)P(S)Cl and (PhO)(2)P(O)Cl, respectively, in the presence of sodium hydride or sodium. Both compounds are Bronsted acids. PCNS forms monoclinic crystals, space group Pc with four crystallographically independent molecules in the asymmetric unit. The skeleton atoms of the molecules form parallel layers via N . . . HN- and S . . . HC-hydrogen bonds. PCNO is orthorhombic, space group Pbca. Its crystal structure is built of ring-shaped dimers via pairs of O . . . HN hydrogen bonds.

Some polydentate μ-imido organophosphorus compounds, in particular bidentate aryl esters of imidodiphosphoric acid, (RO) 2 P(X)NHP(Y)(OR) 2 where X, Y=O or S and R=aryl group can be used as efficient extractants for liquid extraction and separation of many metals. The possibilities of alkaline earth elements extraction (Ca, Ba and Sr) by means of μ-imidophosphorus reagents were studied. The effect of substitution of one ester group by-OH or-NH 2 groups as well as the extraction efficiency of some metals and organic diluents were examined. Significant dimerisation and distribution constants of the reagents were calculated.

The distribution of Ag, Zn, Cd, Sc, Eu, Hg, and Hf between mineral acids (HNO3, HCl) and benzene solutions of selected sulfur derivatives of organophosphoric reagents containing the P(X)NHP(X) or (RO(3))PS group (X = O, S) was examined. The effect of the organic solvent was also investigated for Hg and some of the reagents. The composition of the complexes extracted was identified, and the corresponding extraction constants were calculated.

A reduction of copper(II) to copper (I) occurs in the reaction of N,N-diethyl-N'-diphenooxythiophosphoryl thiourea (C6H5O)(2)P(S)-NH-C(S)-N(C2H5) with Cu2+ in presence of ethanol, and the trinuclear, neutral, diamagnetic chelate complex {Cu-I[(C6H5O)(2)P(S)NC(S)N(C2H5)(2)]}(3) is yielded in form of colourless othorhombic crystals (a = 18.588 Angstrom, b = 25.875 Angstrom, c = 24.881 Angstrom). the lipophilically wrapped polyion aggregate contains a [Cu3S6] nucleus with trigonal planar coordinated copper(I).

The distribution of calcium, strontium, barium and scandium between aqueous and organic phases was studied using 0.1 M HNO 3 or 0.01 to 0.1 M HCl as the aqueous phase and solutions of selected derivatives of organophosphoric reagents containing the conventional =P(O)NHP(O)= bifunctional group or the analogous trifunctional or tetrafunctional group in various organic solvents as the organic phase. The effect of substitution of one ester group by an OH or NH 2 group was examined. While for the alkaline earth metals the distribution ratio increases if the bifunctional group is replaced by a higher-functional group, the reverse is true for scandium. The extraction efficiency is improved by the presence of OH or NH 2 substituent groups. The composition of the extracted species was inferred by logarithmic analysis and the corresponding extraction constants were calculated.

Studies of structure-reactivity relations were carried out in solvent extraction and coordination chemistry of metal ions M(2+) {Na(I), Mg(II), Ca(II), Sr(II), Ba(II), Ln(III) (Sc, Y, La...Lu), Hf(IV), Fe(II), Co(II), Ni(II), Pd(II), Cu(II), Ag(I), Au(III), Zn(II), Cd(II), Hg(II), Tl(I), Pb(II), and Bi(III)} with 38 bi- and tridentate mu-imido organophosphorus compounds with oxygen and sulfur donor atoms. These compounds are Bronsted acids, HA, and form chelate complexes MA(z) in most cases. Different modes of coordination are observed. The extraction of metal ions depends not on only on the set of donor atoms, and the acidity and dimerization constant of the organophosphorus compound. In some cases steric effects are dominant. It was also observed an important influence of the diluent.

An amazingly simple access by dissolving barium metal in tBuOH, addition of nBuLi, and crystallization from THF/hexane leads to the polyion aggregate 1. The novel polyhedral Ba6Li3O2 core has a charge of 11+ and is surrounded by an ellipsoidal C56H123 hydrocarbon skin. Density functional calculations for a 33-center/460-electron model revealed that it is indeed a polyion aggregate, and that weak interactions exist between the two oxygen centers in the polyhedron. In the second communication the hydrocarbon ellipsoid of the polyion aggregate consists of 24 phenyl groups, and the interactions between them are analyzed.

Angewandte ChemieVolume 107, Issue 12 p. 1441-1443 Zuschrift Das lipophil umhüllte Polyionen-Aggregat {H120C144O24[(OP)2N−Na+]6}; ein hexameres Natrium-tetraphenylimidodiphosphat mit einem Na6O12-Kern in einem Kohlenwasserstoff-Ellipsoid†‡ Prof. Dr. Hans Bock, Corresponding Author Prof. Dr. Hans Bock Chemische Institute der Universität, Marie-Curie-Straße 11, D-60439 Frankfurt am Main, Telefax: Int. + 69/5800-9188 Hans Bock, Chemische Institute der Universität, Marie-Curie-Straße 11, D-60439 Frankfurt am Main, Telefax: Int. + 69/5800-9188 Eckhard Herrmann, Hochschule für Technik und Wirtschaft, Josephinen-Straße 1, D-01069 Dresden, Telefax: Int. + 351/4622230Search for more papers by this authorDipl.-Chem. Holger Schödel, Dipl.-Chem. Holger Schödel Chemische Institute der Universität, Marie-Curie-Straße 11, D-60439 Frankfurt am Main, Telefax: Int. + 69/5800-9188Search for more papers by this authorDr. Zdenek Havlas, Dr. Zdenek Havlas Institut für Organische Chemie und Biochemie der Tschechischen Akademie, der Wissenschaften, Prag (Tschechische Republik)Search for more papers by this authorProf. Dr. Eckhard Herrmann, Corresponding Author Prof. Dr. Eckhard Herrmann Hochschule für Technik und Wirtschaft, Josephinen-Straße 1, D-01069 Dresden, Telefax: Int. + 351/4622230 Hans Bock, Chemische Institute der Universität, Marie-Curie-Straße 11, D-60439 Frankfurt am Main, Telefax: Int. + 69/5800-9188 Eckhard Herrmann, Hochschule für Technik und Wirtschaft, Josephinen-Straße 1, D-01069 Dresden, Telefax: Int. + 351/4622230Search for more papers by this author Prof. Dr. Hans Bock, Corresponding Author Prof. Dr. Hans Bock Chemische Institute der Universität, Marie-Curie-Straße 11, D-60439 Frankfurt am Main, Telefax: Int. + 69/5800-9188 Hans Bock, Chemische Institute der Universität, Marie-Curie-Straße 11, D-60439 Frankfurt am Main, Telefax: Int. + 69/5800-9188 Eckhard Herrmann, Hochschule für Technik und Wirtschaft, Josephinen-Straße 1, D-01069 Dresden, Telefax: Int. + 351/4622230Search for more papers by this authorDipl.-Chem. Holger Schödel, Dipl.-Chem. Holger Schödel Chemische Institute der Universität, Marie-Curie-Straße 11, D-60439 Frankfurt am Main, Telefax: Int. + 69/5800-9188Search for more papers by this authorDr. Zdenek Havlas, Dr. Zdenek Havlas Institut für Organische Chemie und Biochemie der Tschechischen Akademie, der Wissenschaften, Prag (Tschechische Republik)Search for more papers by this authorProf. Dr. Eckhard Herrmann, Corresponding Author Prof. Dr. Eckhard Herrmann Hochschule für Technik und Wirtschaft, Josephinen-Straße 1, D-01069 Dresden, Telefax: Int. + 351/4622230 Hans Bock, Chemische Institute der Universität, Marie-Curie-Straße 11, D-60439 Frankfurt am Main, Telefax: Int. + 69/5800-9188 Eckhard Herrmann, Hochschule für Technik und Wirtschaft, Josephinen-Straße 1, D-01069 Dresden, Telefax: Int. + 351/4622230Search for more papers by this author First published: 20. Juni 1995 https://doi.org/10.1002/ange.19951071209Citations: 13 † Lipophil umhüllte Polyionen-Aggregate, 2. Mitteilung, und Wechselwirkungen in Kristallen, 70. Mitteilung. Diese Arbeit wurde von der Adolf-Messer-Stiftung, der Deutschen Forschungsgemeinschaft, dem Land Hessen und dem Fonds der Chemischen Industrie gefördert. –1. bzw. 69. Mitteilung: Lit. [1]. ‡ Professor Peter Schuster gewidmet AboutPDF ToolsRequest permissionAdd to favorites ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article.Citing Literature Volume107, Issue1220. Juni 1995Pages 1441-1443 This is the German version of Angewandte Chemie. Note for articles published since 1962: Do not cite this version alone. Take me to the International Edition version with citable page numbers, DOI, and citation export. We apologize for the inconvenience. RelatedInformation

New O,O',O'',O'' -tetratolyl- and ditolyl-diphenyl-esters of the mu-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by H-1, C-13, and P-31 NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O',O'',O'' -tetrakis-(2-methyl-phenyl)-mu-imido-diphosphate, 1b, as well as of the corresponding ortho-, meta-and para-tolylesters of the mu-imido-monothiodiphospheric acid (2a, 2b, 2c) were determined. All the compounds form dimers via N-H...O hydrogen bonds in the crystal as well as in non polar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the (2)J(P-N-P) coupling constants were determined by C-13{H-1,P-31} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group.

Primary phosphines react with S8 and Se8, respectively, forming organylphosphine monosulfides, and monoselenides, respectively, RP(X)H2 (X = S, Se) which are well characterized by P-31 NMR spectroscopy. Organylphosphine monosulfides are detected in the reaction mixture of primary phosphines with 2,4-diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides, too. The reaction of primary phosphines with sulfur or selenium proceeds in presence of most of the ketones without formation of any side product. The (1-hydroxyalkyl)-organyl-phosphine sulfides and selenides, respectively, RP(X)(H)C(OH)R1R2, are yielded generally in crystalline form. The X-ray crystal structure analysis of the (1-hydroxy-1-methyl-ethyl)-phenyl-phosphane sulfide (R = Ph, R1 = R2 = Me) has shown that in the crystal the molecules are chained via intermolecular 0-H ... S hydrogen bridging bonds (O ... S = 328 pm). Aldehydes react with primary phosphines and sulfur forming bis(I-hydroxyalkyl)-phenyl-phosphine sulfides, RP(S)[CH(OH)R1]2. H-1, C-13 , and P-31 NMR spectroscopic investigations allow to detect and to identify stereoisomers in some cases. Quantumchemical calculations reflect correctly which of the carbonyl compounds are able to react with the organylphosphine monosulfide formed as intermediate.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The extraction of complexes of silver, mercury, cadmium, cobalt, zinc, scandium and some rare earth elements (Ln) into benzene solutions of 1,1-disubstituted 3-diphenoxythiophosphorylthioureas (HA) containing alkyl and aryl substituents was examined using the radiotracer technique. The complexes AgA(HA), HgA2, CdA2 and LnA3 are extracted into the organic phase, and the extraction increases in order Co, Zn, Cd ≈ Ln << Hg < Ag. The extraction constants were calculated. During the extraction process using medium acidic aqueous phases (1 M HNO3), the reagents decompose into the corresponding amines and (PhO)2P(S)NCS.

Secondary and tertiary phosphines (RR'PH; R2R'P) may be synthesized by alkylation of primary or secondary phosphines with organo halides (R' = Et, n-C7H15, Bz, Me3Si; X = Cl, Br) in the presence of Schwesinger bases as auxillary bases in high yields. Alkylation of diphenylphosphine with alkylene dihalides and Schwesinger bases affords alkylendiphosphines. Key Words: Alkylationsecondary and tertiary phosphinesSchwesinger bases

The reaction of M(I)P(SiMe3)2 (M(I) = Li, Na, K) with diorganylchlorophosphines forms tris(diorganylphosphino)phosphines P(PR2)3 (R = Cy, Ph, i-Pr, n-Pr, Et, Me). In all cases, the stepwise formation reaction proceeds via di- and triphosphines resulting in iso-tetraphosphines which are stable in solution. Only the compounds with bulky substituents (R = Cy, Ph) can be isolated. By using quantumchemical procedures it is possible to get information about the pyramidal structure and the reaction behaviour. In agreement with these results orbitally controlled reactions occur where nucleophiles attack the central phosphorus atom.