C-13 AND H-1 NMR STUDIES OF SOLUTION STRUCTURE OF LANTHANIDE COMPLEX WITH GLYCYL-GLYCINE

C-13 and H-1 NMR technique was used to study the interaction of Gly-Gly with heavy lanthanide cations Dy3+, Ho3+, Er3+, Tm3+ and Yb3+ in aqueous solution. The stability constants for the 1:1 and 1:2 complexes of Gly-Gly with Ho3+ and Yb3+ were determined from the titration curves of chemical shift versus concentration ratio of lanthanide to Gly-Gly. The solution structure of the Ln-Gly-Gly complex was analyzed based upon the C-13 and H-1 lanthanide induced shifts and the results show that in the complex Gly Gly is coordinated to the lanthanide ion through the carboxyl oxygens with the backbone of the ligand in an extended state.

SYNTHESIS AND CRYSTAL-STRUCTURE OF A NEW LANTHANIDE CYCLOOCTATETRAENE COMPLEX (ETA-8-C8H8)ER(MU-ETA-8-C8H8)K(MU-ETA-8-C8H8)ER(MU-ETA-8-C8H8)K(THF)4

The tetranuclear nearly-linear complex (eta-8-C8H8)Er(mu-eta-8-C8H8)K(mu-eta-8-C8H8)Er(mu-eta-8-C8H8)K(THF)4 (THF = tetrahydrofuran) is first synthesised by the reaction of benzylcyclopentadienyl erbium dichloride (PhCH2C5H4)ErCl2.3THF with cyclooctatetraenyl potassium K2C8H8 in 1:1 molar ratio in THF; a single crystal X-ray study has shown that the complex has the tetralayer-sandwich structure and that the adjacent Er3+ and K+ ions are bridged by eta-8-cyclooctatetraenyl group.

SYNTHESIS OF ALKALI-METAL HYDRIDES USING LANTHANIDE TRICHLORIDE-NAPHTHALENE AS CATALYST UNDER MILD CONDITIONS

The hydrogenation of alkali metals using lanthanide trichloride and naphthalene as catalyst has been studied. LnCl3(Ln = La, Nd, Sm, Dy, Yb) and naphthalene can catalyze the hydrogenation of sodium under atmospheric pressure and 40-degrees-C to form sodium hydride. The activities of lanthanide trichlorides are in the following order: LaCl3 > NdCl3 > SmCl3 > DyCl3 > YbCl3. Although lithium proceeds in the same catalytic reaction, the kinetic curve of the lithium hydrogenation is different from that of sodium. Lanthanide trichlorides display no catalytic effect on the hydrogenation of potassium in presence of naphthalene. The mechanism of this reaction has been studied and it is suggested that the anion-radical of alkali metal naphthalene complexes may be the intermediate for the hydrogenation of alkali metals and the function of LnCl3 is to catalyze the hydrogenation of the intermediate. The products are porous solids with high specific surface area (83 m2/g for NaH) and pyrophoric in air. They are far more active than the commercial alkali metal hydrides. The combination of these hydrides with some transition metal complexes exhibits high catalytic activity for the hydrogenation of olefins.

SYNTHESIS AND CRYSTAL-STRUCTURE OF HETEROPOLY MOLYBDOSILICIC LANTHANIDE K10H3[PR(SIMO11O39)2].18H2O

The intensity data of the title complex were collected at a low temperature of -90-degrees-C. The compound crystallizes in the monoclinic space group P2(1)/n, a = 17.504(2), b = 27.323 (5), c = 21.616(4) angstrom, beta = 104.49 (2)degrees, Z = 4. The structure was solved by Patterson and Fourier techniques and refined by least-squares to an R = 0.088 for 8320 independent reflections. The central Pr ion is bonded to eight oxygen atoms from two molybdosilicic heteropoly ligands to form a square antiprism. The Pr-O average distance is 2.44 (2) angstrom. Both molybdosilicic heteropoly ligands are of a defective alpha-Keggin structure.

SYNTHESIS OF A NEW TYPE OF CH3CN-COORDINATED LANTHANIDE COMPOUNDS LN(CH3CN)9(ALCL4)3CH3CN

Acetonitrile is a weakly donating ligand. The cationic compounds of CH_3CN-coordinated transition metal are versatile homogeneous catalysts for the polymerization and isomerization of olefins and cycloolefins. The cationic compound of lanthanide[Eu(CH_3·CN)_3(BF_4)_3]_n was prepared from the oxidation of Eu with NOBF_4 in CH_3CN by Thomas in 1986. It was found that [Eu(CH_3CN)_3(BF_4)_3]_n can catalyze the polymerization of styrene cyclohexadiene and other olefins. However, there is no information about...

SYNTHESIS OF TETRAPHENYLBUTADIENE LANTHANIDE METALLACYCLES

The cyclic derivatives of transition metals have been extensively investigated in recent years since they are believed to serve as key intermediates in various homogeneous catalytic processes of olefine and alkyne metathesis. The synthesis of the title compounds has not been reported before.

Preparation of lanthanide hydrides of nanometric size by the catalytic method

Rare-earth metals were hydrogenated in the presence of TiCl4 catalyst in tetrahydrofuran (THF) at 45 degreesC under normal pressure. Transmission electron micrographs showed that the re. sulting lanthanide hydrides were in the form of nanoparticles. The rate of hydrogenation decreased with increasing atomic number of the rare-earth elements.

Synthesis and luminescence properties of lanthanide(III) chelates with polyacid derivatives of thienyl-substituted terpyridine analogues

Two new polyacid derivative ligands of thienyl-substituted terpyridine analogues, N,N,N-1,N-1-[4'-(2"'-thienyl)-2,2':6',2"-terpyridine-6,6"-diyl]bis(methylenenitrilo) tetrakis(acetic acid) (TTTA) and N,N,N-1,N-1-[2,6-bis(3'-amino-methyl-1'-pyrazolyl)-4-(2"-thienyl)pyridine] tetrakis(acetic acid) (BTTA), were synthesized, and the luminescence properties of their Eu3+ and Tb3+ chelates were investigated. The Eu3+ chelates of the two ligands are strongly luminescent having luminescence quantum yields of 0.150 (TTTA-Eu3+) and 0.114 (BTTA-Eu3+), and lifetimes of 1.284 ms (TTTA-Eu3+) and 1.352 ms (BTTA-Eu3+), whereas their Tb3+ chelates are weakly luminescent. The TTTA-Eu3+ chelate was used for streptavidin (SA) labeling, and the labeled SA was used for time-resolved fluoroirnmunoassay of insulin in human sera. The method gives the detection limits of 33 pg ml(-1). (C) 2003 Elsevier B.V. All rights reserved.

UV-blue upconverted emission from Nd3+-doped InF3-based heavy-metal fluoride glasses for blue upconversion fibre laser

We report spectral properties and thermal stability of Nd3+-doped InF3-based heavy-metal fluoride glasses. Fluoroindate glasses in the chemical compositions (in mol%) of (38-x)InF3-16BaF(2)-20ZnF(2)-20SrF(2)-3GdF(3)-1GaF(3-)2NaF-xNdF(3) (x = 0.1, 0.5, 1, 2, 3) have been prepared under a controlled atmosphere in a dry box. Strong UVblue upconversion emission from a green excitation wavelength has been observed and the involved mechanisms have been explained. Near-infrared emission occurs simultaneously upon excitation of the UV-blue upconversion emissions with a cw Ar(+)laser. The upconversion spectra have revealed four dominant emissions at 354, 380, 412 and 449 nm, which belong to the transitions of D-4(3/2) -> I-4(9/2), D-4(3/2) -> I-4(11/2) and P-2(3/2) -> I-4(9/2), D-4(3/2) -> I-4(13/2) and P-2(3/2) -> I-4(11/2), D-4(3/2) -> I-4(15/2) and P-2(3/2) -> I-4(13/2), respectively.