Tetraaquatetrakis(ɛ-caprolactam)lutetium(III) hexaisothiocyanatochromate(III) sesquihydrate

The ionic complex [Lu(?-C₆H₁₁NO)₄(H₂O)₄][Cr(NCS)₆] · 1.5H₂O, the first example of coordination of ?-caprolactam to the lutetium atom, was synthesized by the reaction of Lu(NO₃)₃, K₃[Cr(NCS)₆], and ?-caprolactam in an aqueous solution. The structure of the complex was established by IR spectroscopy and X-ray crystallography. The crystals are triclinic, space group P \(\bar 1\) T = 100 K, a = 11.9604(3) Å, b = 12.3640(3) Å, c = 18.3506(5) Å, α = 91.3200(10)°, β = 108.6640(10)°, γ = 112.4460(10)°, V = 2343.45(10) ų, Z = 2, ρ_calcd = 1.597 g/cm³, R = 0.0299 for 9839 reflections with F _hkl ≥4σ(F). The coordination polyhedron of the lutetium atom is a distorted square antiprism with broken square faces with the oxygen atoms of the organic ligands and water at the vertices. There are weak intramolecular hydrogen bonds N-H…O(H₂) in the cation. The coordination polyhedron of the chromium atom is a somewhat distorted octahedron. The thermal stability of the compound was studied in an inert atmosphere and in air.     

氯冉酸阴离子桥联的Nd(III)-Nd(III), Dy(III)-Dy(III)和 Ho(III)-Ho(III)双 核配合物的合成与磁性

本文合成了三个以氯冉酸阴离子为桥基的稀土双核配合物,Ln~2(Phen)~4(CA)(NCS)~4(Ln=Nd,Dy,Ho;Phen=菲咯啉;CA=氯冉酸二价阴离子)。通过元素分析,红外光谱,电导,电子吸收光谱及变温(4-300K)磁化率表征了配合物,并由变温磁化率观察到的数据和理论方程通过最小二乘法拟合,得出分子内稀土离子间的相互作用参数:Z'J'=-0.79(Nd),-0.67(Dy),-0.63cm^-^1(Ho);表明稀土离子间存在极弱的反铁磁性交换相互作用。零场分裂参数Δ=-0.16(Nd),-0.76(Dy),-2.55cm^-^1(Ho);g=0.618(Nd),1.739(Dy),1.601(Ho),拟合因子≈10^-^4。     

氯冉酸阴离子桥联的Nd(III)-Nd(III), Dy(III)-Dy(III)和 Ho(III)-Ho(III)双 核配合物的合成与磁性

本文合成了三个以氯冉酸阴离子为桥基的稀土双核配合物,Ln~2(Phen)~4(CA)(NCS)~4(Ln=Nd,Dy,Ho;Phen=菲咯啉;CA=氯冉酸二价阴离子)。通过元素分析,红外光谱,电导,电子吸收光谱及变温(4-300K)磁化率表征了配合物,并由变温磁化率观察到的数据和理论方程通过最小二乘法拟合,得出分子内稀土离子间的相互作用参数:Z'J'=-0.79(Nd),-0.67(Dy),-0.63cm^-^1(Ho);表明稀土离子间存在极弱的反铁磁性交换相互作用。零场分裂参数Δ=-0.16(Nd),-0.76(Dy),-2.55cm^-^1(Ho);g=0.618(Nd),1.739(Dy),1.601(Ho),拟合因子≈10^-^4。     

Extraction chromatographic study of aluminium(III) and mutual separation of aluminium(III), gallium(III), indium(III) and thallium(III) with N-n-octylaniline

A selective method has been developed for extraction chromatographic studies of aluminium(III) and its separation from several metal ions with a chromatographic column containing N-n-octylaniline (liquid anion exchanger) coated on silanized silica gel as a stationary phase. The aluminium(III) was quantitatively extracted with the 0.065 mol/L N-n-octylaninine from 0.013 to 0.05 mol/L sodium succinate at a flow rate of 1.0 mL/min. The extracted metal ion has been recovered by eluting with 25.0 mL of 0.05 mol/L hydrochloric acid and estimated spectrophotometrically with aurintricarboxylic acid. The effects of the acid concentration, the reagent concentration, the flow rate and the eluting agents have been investigated. The log-log plots of distribution coefficient (KdAl(III)) versus N-n-octylaniline concentrationin 0.005 and 0.007 mol/L sodium succinate gave theslopes 0.5 and 0.7 respectively and showed theprobable composition of theextracted species was 1:1 (metal to amine ratio) and the nature of extracted species is [RR''NH2+ Al succinate2-] org. .The extraction of aluminium(III) was carried out in the presence of various ions to ascertain the tolerance limit of individual ions. Aluminium(III) has been separated from multicomponent mixtures, pharmaceutical samples and synthetic mixtures corresponding to alloys. A scheme for mutual separation of aluminium(III), indium(III), gallium(III) and thallium(III) has been developed by using suitable masking agents. The method is fast, accurate and precise.     

FERROMAGNETICALLY COUPLED Gd(III)Cu(II)Gd(III)TRINUCLEAR COMPLEXES

ＦＥＲＲＯＭＡＧＮＥＴＩＣＡＬＬＹ ＣＯＵＰＬＥＤ Ｇｄ（ＩＩＩ）Ｃｕ（ＩＩ）Ｇｄ（ＩＩＩ） ＴＲＩＮＵＣＬＥＡＲ ＣＯＭＰＬＥＸＥＳ￥ＭｉｎｇＭｉｎｇＭＩＡＯ；ＤａｉＺｈｅｎｇＬＩＡＯ；ＺｏｎｅＨｕｉＪＩＡＮＧ；ａｎｄＧｅｎｇＬｉｎＷＡＮＧ（Ｄｅｐ...     

Complexation of Sc(III), Ga(III), In(III) and Ln(III) with Eriochrome Red B

Cyclic linear-sweep voltammetry was used to study the complexation of Sc(III), Ga(III), In(III) and Ln(III) with eriochrome red B (ERB). It was established that all metal ions investigated form complex compounds with azodye having a mole ratio, M(III):ERB = 1:2. The hydroxo forms of M(III) ions, which take part in interaction with ERB, were determined by the Nazarenko method. The stability constants for the formation of these chelates are nearly the same. It was shown that the reduction of the ligand in the complex does not only depend on the peculiarities of complexation, but the processes occurring in pre-electrode layer also influence it.     

Transport behaviour of the lanthanide 152Eu(III), 153Gd(III) and 170Tm(III) and transplutonium element 254Es(III), 244Cm(III), 241Am(III), 249Cf(III) and 249Bk(III) ions in aqueous solutions at 298 K

Ionic self-diffusion coefficients (D) for trivalent radiotracers, lanthanide and actinide ions have been determined in concentrated aqueous solutions of supporting electrolytes of Gd(NO₃)₃–HNO₃ or Nd(ClO₃)₄–HClO₄ up to 1.5 mol L^?1 at 298.15 K and pH 2.50 by the open-end capillary method. The data obtained in large range of concentrations, allow to derive the limiting value D°, the validity of the Onsager limiting law and a more extended law. This study contributes to demonstrate similarities in transport and structure properties between 4f and 5f trivalent ions explained by a similar electronic configuration, ionic radius and hydration number. An empirical equation is suggested for predicting ionic hydration number with a good precision.     

Syntheses of (imidazole)pentaamminemetal(III) and μ-imidazolatodecaamminedimetal(III) complexes from trifluoromethanesulfonato precursors

The [M(NH₃)₅(imidH)]³⁺ complex ions (M = Co, Rh or Ir; imidH = imidazole) can be readily prepared by reaction of [M(NH₃)₅(OSO₂CF₃)]²⁺ ions with imidazole in sulfolane. Subsequent reaction of [M′(NH₃)₅(OSO₂CF₃)]²⁺ with [M(NH₃)₅(imidH)]³⁺ in sulfolane in the presence of a non-coordinating base permits synthesis of the binuclear imidazolate-bridged complexes [(NH₃)₅M(imid)M′(NH₃)₅]⁵⁺ (M = M′= Co or Rh; M = Co, M′ = Rh), characterized by spectroscopic, chromatographic and voltammetric methods, and by reactivity.     

Octa(ɛ-caprolactam)erbium(III) hex(isothiocyanato)chromate(III): Synthesis and crystal structure

The ionic mixed-ligand bimetallic complex [Er(?-C₆H₁₁NO)₈][Cr(NCS)₆] has been synthesized and studied by X-ray diffraction analysis. The crystals are monoclinic, space group C2/c, a = 39.627(2) Å, b = 22.3406(11) Å, c = 23.7155(10) Å, β = 107.687(2)°, V = 20 002.9(16) ų, Z = 12, ρ_calcd = 1.467 g/cm³. The coordination polyhedron of the erbium atom is a distorted square antiprism formed by the oxygen atoms of the organic ligands. The Er-O bond lengths vary within 2.29–2.44 Å. The coordination polyhedron of the chromium atom is a slightly distorted octahedron, and the Cr-N bond lengths range from 1.99 to 2.01 Å.     

Polynuclear Heteroligand Yb(III)–Er(III) Complexes as Potential Upconversion Materials

Russian Journal of Coordination Chemistry - The synthesis of complexes LnI(C6F5O)2 and LnCp(L)2 (Ln = Er, Yb; L = C6F5O, SONF), which are convenient precursors for the preparation of heteroligand...     

Mit Cer(III)-Sulfatl?sungen lassen sich Hexacyanoferrat(III) und Permanganat

Ohne Zusammenfassung     

Thermal analysis of rare-earth metal(III) hexa(isothiocyanato)chromate(III) complexes with ɛ-caprolactam

Thermal decomposition of the complexes [LnL₈][Cr(NCS)₆] (Ln = La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺, Tm³⁺, Yb³⁺, Lu³⁺; L = ɛ-C₆H₁₁NO) in air and in inert atmosphere was studied by thermogravimetry, X-ray phase analysis, IR spectroscopy, and mass spectrometry. The compositions of gaseous and solid thermolysis products were established. A reversible thermochromic effect was found on heating to 200–210°C.     

Ferrocene-containing ligands in the self-assembly of trinuclear μ3-oxocentered carboxylate complexes of chromium(III, III, III)carboxylate complexes of chromium(III, III, III)

New trinuclear μ₃-oxocentered chromium(III, III, III) complexes were obtained by the self-assembly of ferrocenecarboxylate ligands and the Cr₃O fragment. The complexes were investigated by fast-atom bombardment (FAB) mass spectrometry, cyclic voltammetry, and electronic and IR spectroscopy. V. I. Vernadskii Institute of General and Inorganic Chemistry, National Academy of Sciences of Ukraine, 32/34 Prospekt Akademika Vernadskogo, Kiev 03142, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 36, No. 4, pp. 233–237, July–August, 2000.     

σ-Bonded organometallic derivatives of yttrium(III) and thulium(III): An unusual ligand coupling reaction mediated by thulium(III)

The reaction between LnI₃(THF)_3.5 and 2 equiv. of {(Me₃Si)₂(Me₂MeOSi)C}K (1) in THF at room temperature yields only the mono-substituted products {(Me₃Si)₂(Me₂MeOSi)C}LnI₂(THF)₂ [Ln = Y (5), Tm (6)]; under more forcing conditions decomposition occurs. In contrast, the metathesis reaction between TmI₃(THF)_3.5 and 2 equiv. of the lithium iodide-containing salt {(Me₃Si)₂(Me₂MeOSi)C}K(LiI)_x yields the highly unusual separated ion pair complex [[{(Me₃Si)₂C(SiMe₂)}₂O]TmI₂{Li(THF)₃}₂][[{(Me₃Si)₂C(SiMe₂)}₂O]TmI₂] (8). The dianionic ligand in 8 is derived from the coupling of 2 equiv. of (Me₃Si)₂(Me₂MeOSi)C⁻, accompanied by the formal elimination of Me₂O. The structures of compounds 5, 6, and 8 have been determined by X-ray crystallography; compound 8 crystallizes as an unusual ion pair, the cation and anion of which differ only in the inclusion of 2 equiv. of Li(THF)₃ in the former, bridged to thulium by iodide ions.     

Über Vanadium(III)-hydroxyd

Zusammenfassung Durch Reduktion von Natriumvanadatlösungen an einer großflächigen Hg-Kathode läßt sich unter Sauerstoffausschluß Vanadium(III)-hydroxyd als kristalline bronzefarbene, leicht oxydable Verbindung gewinnen.Mit 3 AbbildungenHerrn Prof. Dr.F. Wessely zum 60. Geburtstag gewidmet.     

Planar tetranuclear Dy(III) single-molecule magnet and its Sm(III), Gd(III), and Tb(III) analogues encapsulated by salen-type and β-diketonate ligands

The syntheses, structures, and magnetic properties are reported for four new lanthanide clusters [Sm(4)(μ(3)-OH)(2)L(2)(acac)(6)]·4H(2)O (1), [Gd(4)(μ(3)-OH)(2)L(2)(acac)(6)]·4CH(3)CN (2), and [Ln(4)(μ(3)-OH)(2)L(2)(acac)(6)]·2H(2)L·2CH(3)CN (3, Ln = Tb; 4, Ln = Dy) supported by salen-type (H(2)L = N,N'-bis(salicylidene)-1,2-cyclohexanediamine) and β-diketonate (acac = acetylacetonate) ligands. The four clusters were confirmed to be essentially isomorphous by infrared spectroscopy and single-crystal X-ray diffraction. Their crystal structures reveal that the salen-type ligand provides a suitable tetradentate coordination pocket (N(2)O(2)) to encapsulate lanthanide(III) ions. Moreover, the planar Ln(4) core is bridged by two μ(3)-hydroxide, four phenoxide, and two ketonate oxygen atoms. Magnetic properties of all four compounds have been investigated using dc and ac susceptibility measurements. For 4, the static and dynamic data indicate that the Dy(4) complex exhibits slow relaxation of the magnetization below 5 K associated with single-molecule magnet behavior.     

Die Bestimmung von Cer(III) durch Titration mit Hexacyanoferrat(III)-l?sung

Ohne Zusammenfassung     

Koordinationsverhältnisse in basenfreien tricyclopentadienyl-lanthanoid(III)-komplexen: IV. Die röntgenstrukturen von tricyclopentadienyl-erbium(III) und -thulium(III)

The single crystal X-ray analyses of sublimated (C₅H₅)₃Er (6) and (C₅H₅)₃Tm (7) confirm, for the first time, the existence of coordinatively well-saturated molecules containing just three η⁵-C₅H₅ ligands per metal ion (formal coordination number: 9, space group: Pna2₁, lattice parameters: a 1972.1(3), b 1389.4(1), c 862.4(3) pm for 6, and a 1999.1(3), b 1379.8(4), c 1379.8(4), c 857.8(3) pm for 7; R = 0.076 and 0.047, respectively). Individual molecules align themselves into chains by Van der Waals interactions. The structures of 6 and 7 show a marked contrast to those of their La und Pr homologues on the one hand, and with the structure of (C₅H₅)₃Lu on the other.     

Gold(III) π-Allyl Complexes

Gold(III) π-complexes have been authenticated recently with alkenes, alkynes, and arenes. The key importance of Pd^II π-allyl complexes in organometallic chemistry (Tsuji–Trost reaction) prompted us to explore gold(III) π-allyl complexes, which have remained elusive so far. The (P,C)Au^III(allyl) and (methallyl) complexes 3 and 3′ were readily prepared and isolated as thermally and air-stable solids. Spectroscopic and crystallographic analyses combined with detailed DFT calculations support tight quasi-symmetric η³-coordination of the allyl moiety. The π-allyl gold(III) complexes are activated towards nucleophilic additions, as substantiated with β-diketo enolates.