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1.
The preparation and some properties of the cobalt(II) complexes Co(LH2)Cl2·2H2O, Co(LH2(NCS)2 and CoL·H2O (whereLH2=N,N-(dipicolyl)-1,8-naphthylenediamine) are reported. On the basis of magnetic moments, visible reflectance and IR data, the structure is proposed to be pseudo-octahedral for Co(LH2)Cl2·2 H2O, pseudo-tetrahedral for Co(LH2)(NCS)2 and square planar for CoL·H2O.
Deprotonierte und Nicht-deprotonierte Co(II)-Komplexe des vierzähnigen Bisamid-Liganden N,N-(Dipicolyl)-1,8-naphthyldiamin. Drei verschiedene Koordinationstypen
Zusammenfassung Es werden die Darstellung und einige Eigenschaften der Kobalt(II)-Komplexe Co(LH2)Cl2·2 H2O, Co(LH2)(NCS)2 und CoL·H2O [LH2=N,N-(dipicolyl)-1,8-naphthylendiamin] diskutiert. Auf der Grundlage von magnetischen Momenten, von Daten der sichtbaren Reflektions-und IR-Spektren wird eine pseudooctaedrische Struktur für Co(LH2)Cl2·2H2O, eine pseudotetraedrische für Co(LH2)(NCS)2 und eine planar-quadratische für CoL·H2O vorgeschlagen.
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2.
The preparation of a series of new compoundsLnBr3(2-bipy)2·6H2O (Ln=La, Pr, Nd, Eu, Gd) andLnBr2OH(2-bipy)2·4H2O (Ln=Pr, Nd, Sm, Eu, Gd) is described. The IR spectra of these compounds are discussed. The thermal decomposition of compoundsLnBr3(2-bipy)2·6H2O has been investigated.
2,2-Bipyridylkomplexe einiger Seltenerdmetallbromide
Zusammenfassung Es wurden 2,2-Bipyridylkomplexe des TypsLnBr3(2-bipy)2·6H2O (Ln=La, Pr, Nd, Sm, Eu, Gd) undLnBr2OH(2-bipy)2·4H2O (Ln=Pr, Nd, Sm, Eu, Gd) dargestellt. Die IR-Spektren werden diskutiert. Die thermische Zersetzung von VerbindungenLnBr3(2-bipy)2·6H2O wird untersucht.
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3.
The intercalation reactions betweenn-alkylamines and -titanium phosphate in aqueous media have been investigated. The compounds with the maximum intercalation have the formula -Ti(HOPO3)2 · 2 C n H 2n+1 NH2 · H2O (n=1–10). Defined crystalline phases with lower amine content are described, the general formula being -Ti(HOPO3)2 · m C n H 2n+1 NH2 ·pH2O (m=1.0 1.3, 1.5, 1.7). Whenm=1.0 then-alkylamines form a monomolecular layer. Whenm>1.0 the layer is bimolecular. The inclination angle and the packing density of then-alkylamines in the interlayer space is determined.  相似文献   

4.
Solubility properties of the ternary systems of Cr(NO3)3–His–H2O, Cr(NO3)3–Met–H2O, and CrCl3–His–H2O (His—histidine, Met—methionine) have been investigated in the whole concentration range by the phase equilibrium semimicromethod, and the corresponding phase diagrams have been constructed. It was shown that the new complexes Cr(His)(NO3)3 · 3H2O, Cr(His)2(NO3)3 · 3H2O, Cr(His)3(NO3)3 · 3H2O, Cr(His)Cl3 · H2O, Cr(His)2Cl3 · H2O, and Cr(His)3Cl3 · H2O are formed in the Cr(NO3)3/CrCl3–His–H2O system, while Cr(Met)(NO3)3 · H2O and Cr(Met)2(NO3)3 · H2O complexes are formed in the system Cr(NO3)3–Met–H2O. Under the guidance of the phase diagrams, the complexes were prepared and characterized by chemical and elemental analysis, IR spectroscopy, and thermogravimetry data. The influences of metal cations, anions and the structures of amino acids on the formation of complexes were discussed.  相似文献   

5.
Four copper(II) complexes of betaines, [Cu2(BET)4Cl2][Cu(BET)2Cl2]Cl2 (2), [Cu2(pyBET)4Cl2]3[CuCl4]2Cl2 (3), [Cu, (pyBET)4 (H2O)2] (NO3)4 · 2H2O (4), and [Cu2(ppBET)4(H2O)2](ClO4)4 · 4H2O (5), (BET = Me3N+CH2COO; pyBET = C5H5N+CH2COO; ppBET=C5H5N+CH2CH2COO), have been prepared and characterized by X-ray crystallography. These complexes all contain dimeric [Cu2 (carboxylato-O,O)4L2] structures [basal Cu-O=1.955(4) 1.991(2), Cu Cu=2.602(1) 2.759(1) Å] with the apical ligand L=Cl in (2) and (3) [Cu-Cl=2.415(1) 2.436(3) Å] and L = H2O in (4) and (5) [Cu-OH2=2.158(4) 2.192(3) Å]; also present are a discrete [Cu(BET)2Cl2] molecule with a compressed tetrahedral CuO2Cl2 chromophore involving two unidentate carboxylate ligands [Cu-O=1.916(2), Cu-Cl=2.254(1) Å] in (2), and a discrete C3v [CuCl4]2– anion in (3). Generally the intradimer Cu Cu distance may be correlated to the electronic repulsion of the metal-ligand bonds in the CuO4L chromophore, as well as the steric interaction between the carboxylate moieties and the apical ligand.  相似文献   

6.
The intercalation of phenylethylamines into-zirconium phosphate has been investigated by the pH titration method.dl-1-Phenylethylamine (dl-PEA) is taken up in two stages. New phases were obtained: Zr(HPO4)2(dl-PEA) · H2O in the first, and Zr(HPO4)2(dl-PEA)/43· H2O in the second stage. 2-Phenylethylamine (2-PEA) also is loaded in two stages, but the first end point is not observed clearly. A new phase, Zr(HPO4)2(2-PEA)2 · H2O has been formed at the second stage. The new phases have been characterized by elemental analysis, X-ray diffractometry, thermal analysis and IR spectroscopy.  相似文献   

7.
4,4-Dipyridyl and 2,2-dipyridyl complexes of rare-earth perchlorates of the formulaLn(4-dipy)8(ClO4)3HClO4 · 4H2O (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 4-dipy=4,4-dipyridyl) andLn(2-dipy)3(ClO4)3 · 6H2O (Ln=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 2-dipy = 2,2-dipyridyl) have been synthesized. The IR spectra of these compounds and other physical properties are discussed.
4,4-Dipyridyl- und 2,2-Dipyridylkomplexe von Seltenerdmetallperchloraten
Zusammenfassung Es wurden 4,4-Dipyridylkomplexe des TypsLn(4-dipy)8(ClO4)3HClO4 · · 4 H2O mitLn=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y und 2,2-Dipyridylkomplexe des TypsLn(2-dipy)3(ClO4)3 · 6 H2O mitLn=Pr, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu und Y dargestellt. Die IR-Spektren und andere physikalische Eigenschaften werden diskutiert.
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8.
Summary The use of ethyl oxamate for the synthesis of inorganic oxamato complexes is reported. A reaction system leading to the preparation of the novel polymeric -oxamato(-2) complexes [M(oxm)(H2O)2] x (M=Cu, Zn, Cd), [Co(oxm)(H2O)2] x ·0.5xH2O and [Ni(oxm)(H2O)2] x ·xH2O is described (H2 oxm = oxamic acid). Ethyl oxamate can also be used for the preparation of monomeric oxamato(-1) complexes.
Der Einsatz von Ethyloxamat für die Synthese von Oxamato(-1) und neuen -Oxamato(-2)-Komplexen (Kurze Mitt.)
Zusammenfassung Es wird der Einsatz von Ethyloxamat für die Synthese von anorganischen Oxamato-Komplexen beschrieben. Ein Reaktions-System für die Herstellung von neuen -Oxamato(-2)-Komplexpolymeren: [M(oxm)(H2O)2] x ; (M = Cu, Zn, Cd), [Co(oxm)(H2O)2] x ·0.5xH2O und [Ni(oxm)(H2O)2] x ·xH2O, wird vorgestellt. Ethyloxamat kann auch für die Herstellung von monomeren Oxamato(-1)-Komplexen verwendet werden.
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9.
2,4-Bipyridyl (2,4-bipy orL) complexes with cobalt(II), nickel(II) and copper(II) of the formulae M(2,4-bipy)2(CH3COO)2·2H2O (M(II) = Co, Ni, Cu), Co(2,4-bipy)2SO4·3H2O or Ni(2,4-bipy)2SO4·4H2O have been prepared and their IR and electronic (VIS) spectra are discussed. The thermal behaviour of the obtained compounds has also been studied. The intermediate products of decomposition at different temperatures have been characterized by chemical analysis and X-ray diffraction.We thank dr. A. Malinowska for performing VIS spectra. This work was supported by the KBN project No. PB 0636/P3/93/04.  相似文献   

10.
Summary The following coordination compounds derived from 2-guanidinobenzimidazole (2GB) (1); [Ni(2GB)2]Cl2· H2O, (2); [Ni(2GB)2]Br2·3H2O, (3); [Ni(2GB)2-(NO3)2, (4); [Ni(2GB)2](OAc)2, (5); [Cu(2GB)Cl2], (6); [Cu(2GB)Br2], (7); [Cu(2GB)2]Br2·2H2O, (8); [Cu(2GB)2](NO3)2·H2O, (9); [Cu(2GB)2](OAc)2· H2O, (10); [Zn(2GB)Cl2]·H2O, (11); [Zn(2GB)Br2]·H2O, (12); [Co(2GB)Cl2(H2O)2]·5H2O, (13); [Co-(2GB)2Cl2]·3H2O, (14); [Co(2GB)2(H2O)2](NO3)2· 4H2O, (15); and [Co(2GB)2(H2O)2](OAc)2, (16) have been synthesized and characterized by i.r. and electronic spectroscopy. In addition (6)–(10) were analysed by e.p.r. The X-ray diffraction structure of compound (4) was obtained. It crystallizes in the monoclinic system, C2/c (a = 22.511(7), b = 6.735(6) and c= 15.345(5)Å, =115.31(3)°, Z = 4, final R = 0.0360 and R w = 0.0388 for 1167 observed independent reflections). The nickel(II) atom coordinates two ligands in a square-planar geometry through the imidazolic N(3) and the guanidino N(12).The probable ligand isomers involved in the coordination were determined by theoretical calculations, and the possible structures of the coordination compounds were investigated in order to verify that the experimentally proposed structures were stable. Two different types of coordination compounds were found. One, where the ligand is chelating through the imidazolic N(3) and the guanidino N(12), which is the case for most of the complexes [(2)–(13)]. With only one ligand in the coordination sphere, the structure was either tetrahedral (copper and zinc chloride and bromide complexes) or octahedral (cobalt). With two chelating 2GB units a square-planar geometry was stabilized [(2)–(5) and (8)–(10)]. The second type of coordination behaviour was observed in the cobalt compounds [(14)–(16)]. Here the ligand coordinates monodentate through the imidazolic N(3); the structure is tetrahedral.  相似文献   

11.
Summary The Schiff base ligand diethyl(ethylenebis--aminocrotonate) (LH2) reacts with lanthanide(III) chlorides and nitrates in various solvents to give solid complexes of the stoichiometriesLn(LH2)Cl3 (Ln=La–Yb),Ln(LH2)2Cl3 (Ln=La–Sm),Ln 2(LH2)3Cl6(Ln=Eu–Yb) andLn(LH2)(NO3)3 (Ln=La–Yb). Properties, conductivity measurements, X-ray powder patterns, thermal data, magnetic moments and spectroscopic (IR,1H-NMR, electronic diffuse reflectance and solid state emission f-f spectra) are discussed in terms of the nature of the bonding and the possible structural types.
Synthese und Charakterisierung der Komplexe von Lanthanid(III)chloriden und -nitraten mit der vierzähnigen Schiff-Base Diethyl(ethylenbis--aminocrotonat)
Zusammenfassung Der Schiffbasen-Ligand Diethyl(ethylenbis--aminocrotonat) reagiert mit Lanthanid(III)chloriden und -nitraten in verschiedenen Lösungsmitteln unter der Bildung von festen Komplexen der StöchiometrienLn(LH2)Cl3 (Ln = La – Yb),Ln(LH2)2Cl3 (Ln = La – Sm),Ln(LH2)3Cl6 (Ln = Eu – Yb) undLn(LH2)(NO3)3 (Ln = La – Yb). Die allgemeinen Eigenschaften, Leitfähigkeitsmessungen, Röntgen-Pulverdiagramme, thermische Daten, magnetische Momente und spektroskopische Daten (IR,1H-NMR, Elektronenreflexionsspektren und Festkörperemissions-f-f-Spektren) werden im Hinblick auf die Bildungsverhältnisse im Komplex und strukturelle Möglichkeiten diskutiert.
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12.
4,4-Dipyridyl complexes of rare-earth thiocyanates of the formulaLn(4-dipy)2(NCS)3·5H2O (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Y, 4-dipy = 4,4-dipyridyl) have been synthesized. The IR spectra of these compounds and other physical properties are discussed. The thermal decomposition of some compounds (in the order Gd ÷ Lu) has been investigated.
4,4-Dipyridylkomplexe von Seltenerdmetallthiocyanaten
Zusammenfassung Es wurden 4,4-Dipyridylkomplexe des TypesLn(4-dipy)2(NCS)3·5H2O mitLn = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu und Y dargestellt. Die IR-Spektren und andere physikalische Eigenschaften werden diskutiert und die thermische Zersetzung von einigen Verbindungen (in der Reihe Gd ÷ Lu) untersucht.
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13.
Gamma-ray induced decomposition of some divalent nitrates, viz. Mg(NO3)2·6H2O, Ca(NO3)2·4H2O, Sr(NO3)2, Ba(NO3)2, Zn(NO3)2·6H2O, Cd(NO3)2·4H2O, Hg(NO3)2·2H2O, Mn(NO3)2·4H2O, Cu(NO3)2·3H2O and trivalent nitrates, viz. Al(NO3)3·9H2O, Fe(NO3)3·9H2O, Cr(NO3)3·9H2O, Y(NO3)3·6H2O, In(NO3)3·3H2O, La(NO3)3·6H2O, Ce(NO3)3·6H2O, Pr(NO3)3·6H2O, Bi(NO3)3·5H2O has been studied in solid state at room temperature. G(NO 2 ) values (after applying appropriate dose correction) have been found to vary in the range 0.12–3.16 and 0.069–2.15 for divalent and trivalent nitrates respectively. G'-values were calculated by dividing G by the ratio of number of electrons in nitrate ion to the total number of electrons in the nitrate salt. Cation size, its polarizing power, available free space in the crystal lattice and the number and location of water molecules seem to play a dominant role in radiolytic decomposition. For Zn, Sr, In, La and Ce nitrates dose variation studies have been carried out.  相似文献   

14.
The solubility property of Zn(NO3)2–Thr–H2O system (Thr—threonine) at 25°C in the entire concentration range has been investigated by the phase equilibrium semimicromethod. The corresponding phase diagram and refractive index diagram were constructed. From the phase equilibrium results, the incongruently soluble compounds of Zn(Thr)(NO3)2 · 2H2O, Zn(Thr)2(NO3)2 · H2O, and Zn(Thr)3(NO3)2 · H2O were synthesized and characterized by IR, XRD, TG–DTG, chemical and elemental analyses. The constant-volume combustion energies of the compounds, c E, determined by precision rotating bomb calorimeter at 298.15 K, were –6266.88 ± 3.72, –9263.28 ± 2.23, and –11 423.11 ± 6.81 J/g, respectively. The standard enthalpies of combustion for these compounds, c H m ° (complex, s., 298.15 K), were calculated as –2147.40 ± 1.28, –4120.83 ± 0.99, and –6444.68 ± 3.85 kJ/mol and the standard enthalpies of formation, f H m ° (complex, s., 298.15 K), are –1632.82 ± 1.43, –1885.55 ± 1.50, and –2770.25 ± 4.21 kJ/mol. The enthalpies of dissolution of the complexes in a medium of simulated human gastric juice (37°C, pH 1, in the solution of hydrochloric acid), dis H m ° (complex, s., 310 K), which were also measured by a microcalorimeter to be 13.36 ± 0.06, 15.53 ± 0.06, and 17.04 ± 0.05 kJ/mol, respectively.  相似文献   

15.
Compounds ScL 2(NO3)3·2 H2O,LnL 2(NO3)3·H2O (Ln=Pr, Sm, Eu, Gd, Tb),LnL 2(NO3)3·3 H2O (Ln=Nd, Dy, Ho, Er),LnL 3(NO3)3 (Ln=Pr, Nd) andLnL 3(NO3)3· ·3 H2O (Ln=Sc, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were isolated. They were investigated by means of thermoanalysis, IR spectroscopy, X-ray diffraction and molar conductivity.

L=2,2-Bipyridin-N,N-dioxid=bpyO2=C10H8N2O2.  相似文献   

16.
The general thermochemical reaction LnCl3·6H2O(c)+3Hthd(1)+73.92H2O(1) = Ln(thd)3(c) +3HCl·26.64H2O(aq); rHm (Ln = Pr, Ho and thd = 2,2,6,6-tetramethyl-3,5-heptanedionate) was employed to determine through solution-reaction calorimetry at 298.15 K the standard molar enthalpies of formation of crystalline chelates, –2434.3±11.5 (Pr) and –2384.8±11.5 (Ho) kJ mol–1. These values and the corresponding molar enthalpies of sublimation enabled the determination of the standard molar enthalpies of chelates in the gaseous phase. From these values the mean enthalpies of the lanthanide-oxygen bond, 265±10 (Pr) and 253±10 (Ho) kJ mol–1 were calculated.  相似文献   

17.
Phosphorus hydrazides PhP(O)[N(Me)NH2]2, (S)P[N(Me)NH2]3, and N3P3[N(Me)NH2]6 were condensed with 7-diethylaminocoumarin-3-aldehyde (RCHO) to afford the corresponding hydrazones PhP(O)[N(Me)NCHR]2 (1), (S)P[N(Me)NCHR]3 (2), and N3P3[N(Me)NCHR]6 (3). The structural characterization of 1-3 was carried out by their HRMS, 1H and 31P{1H} NMR spectra. The molecular structure of 2 was established by a single-crystal X-ray analysis. Interaction of 1 and 2 with various transition metal ions revealed substantial fluorescence enhancement upon interaction with Cu2+ enabling a selective detection mechanism for this metal ion. However, such a fluorescence enhancement was not observed in the case of 3. A 1:1 complex [2·Zn][ClO4]2·4CH2Cl2 was isolated in the reaction of 2 with Zn(ClO4)2·6H2O. The molecular structure of this complex revealed that the ZnII is encapsulated by the ligand utilizing a 3N, 3O coordination set.  相似文献   

18.
Ultrafine metal particles (UFMP) (iron and cobalt) have been obtained in solid-state redox reactions of cyclopentadienyl--(3)-1,2-dicarbollyliron or cyclopentadienyl--(3)-1,2-dicarbollylcobalt with elemental sulfur ((C5H5)Fe3+(C2B9H11)-S, (C5H5)Co5+C2B9H11-S). These reactions are realized by the action of elastic wave (EW) pulses on powder compositions of these substances. Study of the UFMP obtained by the ferromagnetic resonance (FMR) method has shown that the sizes ofn · Co0 UFP lie in the range from 1 to 13 nm. UFP of cobalt and iron are also formed under the action of EW on samples containing (C5H5)Fe3+(C2B9H11)-S or (C5H5)Co3+(C2B9H11)-S within the film of tetrafluoroethylene and perfluoro-4-methyl-3,6-dioxaoct-7-ene-1-sulfonyl fluoride copolymer (CP). It is shown by the FMR method that FMR lines broaden on going from powder systems to systems containing CP films. It is supposed thatn · Co0 and n · Fe0 particles interact with polymeric matrices in the course of formation and stabilization of UFMP in the matrices.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2355–2358, December, 1995.This work was financially supported by the Russian Foundation for Basic Research (Project No. 94-03-09632).  相似文献   

19.
Compounds of the composition La(bpyO2 *)4Cl3·4H2O, La(bpyO2)3Cl3·5H2O, La(bpyO2)2Cl3·3H2O, La(bpyO2)Cl3·3H2O, La(bpyO2)4Br3·4H2O, La(bpyO2)3Br3·8H2O, La(bpyO2)2Br3·7H2O, La(bpyO2)Br3·4H2O, La(bpyO2)4I3·3H2O, La(bpyO2)3(NO3)3·2H2O, La(bpyO2)2(NO3)3·2H2O, La(bpyO2)4(SCN)3·3H2O, La(bpyO2)3(SCN)3·2H2O, La(bpyO2)2(SCN)3·2H2O were isolated. They were investigated by means of thermoanalysis, I.R. spectroscopy, X-ray diffraction and molar conductivity.  相似文献   

20.
Monomers which contain unsaturated linkages and amine groups have been intercalated to form either mono- or bi-layers. The monomertrans-N,N-diethyl-2-butene-1,4-diamine (NNBD) has been intercalated into -tin(IV) hydrogen phosphate. The guest molecule, NNBD, forms a monolayer (d 001 = 1.35 nm) in which the amine groups are paired to protons on opposite faces of the phosphate layers. The resultant compound has the formula Sn(C8H18N2)0.73(HPO4)2·H2O indicating that NNBD does not cover a large proportion of the available protons. 4-vinylpyridine slowly forms an intercalate in which the host molecule forms a bilayer (d 001 = 1.56 nn). However, with 4-vinylpyridine there is surface modification in preference to intercalation.  相似文献   

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