A. V. Safronova

β-Diketonate heteroligand complex of terbium and polymer material on its basis. synthesis, photo-, and electroluminescent properties

New β-diketonate heteroligand complex of terbium is synthesized. On its basis, using the method of metathesis polymerization, a terbium-containing polymer has been prepared. The synthesized polymer material forms nanodimensional films possessing photo- and electroluminescent properties.

Synthesis and structures of silicon-, germanium-, and tin-containing tungsten carbyne complexes (ButO)3W≡C—EPh3 and [(ButO)3W≡C]2EPh2 (E = Si, Ge, Sn)

New tungsten carbyne complexes (ButO)3W≡C—SiPh3, [(ButO)3W≡C]2SiPh2, [(ButO)3W≡C]2GePh2, and [(ButO)3W≡C]2SnPh2 were prepared by the reactions of (But)6W2 with Ph3SiC≡C—Pr or Ph2E(C≡C—Pr)2 (E = Si, Ge, Sn) in individual crystalline form in 48—80% yields. The structures of both the (ButO)3W≡C—GePh3 and (ButO)3W≡C—SnPh3 compounds synthesized earlier and the new complexes were established by X-ray diffraction analysis.

Thermodynamic characteristics of neodymium and terbium pyrazolonate complexes

The sublimation of 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolonate complexes of neodymium and terbium was studied by the Knudsen effusion method with mass spectrometric gas phase monitoring. The gas phase was shown to contain only monomeric molecular species. The sublimation enthalpy (kJ/mol) for Nd complex is 205.9 ± 2.7 and that for the Tb complex is 208.0 ± 4.0.

5-{5-(bicyclo[2.2.1]hept-2-enyl)hydroxymethyl}-3,6-di-tert-butylo-benzoquinone and related polymers. Synthesis and some properties

A norbornene-containing ortho-quinone, 5-{5-(bicyclo[2.2.1]hept-2-enyl)hydroxymethyl)-3,6-ditert-butyl-o-benzoquinone, was synthesized by the nucleophilic addition of 5-(hydroxymethyl)bicyclo[2.2.1] hept-2-ene to 3,6-di-tert-butyl-o-benzoquinone. The structure of the compound was established by the X-ray analysis. The monomer obtained undergoes metathesis polymerization in the presence of Grubbs catalyst of the third generation with the formation of polynorbornene containing quinone fragments in the side chains.

Synthesis, structure, and some properties of 1-phenyl-3-methyl-4-(2,3,4,5,6-pentafluorobenzoyl)pyrazol-5-one and its lanthanide complexes

A new 4-acylpyrazolone—1-phenyl-3-methyl-4-(2,3,4,5,6-pentafluorobenzoyl)-1H-pyrazole-5(4H)-one (Pfb-PMPH)—was prepared in a high yield by the reaction of 1-phenyl-3-methylpyrazol-5-one with pentafluorobenzoyl chloride in the presence of calcium and barium hydroxides. On heating this compound in vacuum up to 170°C, elimination of HF takes place to give the intramolecular cyclization product, 1-phenyl-3-methyl-5,6,7,8-tetrafluorochromeno[2,3-c]pyrazol-4(1H)-one. The structures of Pfb-PMPH (HL1) and the cyclization product (L2) were determined by X-ray diffraction (CIF files CCDC nos. 1010331 (HL1), 1010332 (L2), 1010333 (VI), 1010334 (VII), 1010335 (VIII), 1010336 (IX), and 1010337 (X)). The reactions of Pfb-PMPH with lanthanide silylamides [(Me3Si)2N]3Ln in a THF solution give pyrazolonate complexes (Pfb-PMP)3Ln(THF) (Ln = Sm, Eu, Gd, Tb, Lu). The compounds react with Ph3PO to give the derivatives (Pfb-PMP)3Ln(OPPh3)2 · xEtOH, which were studied by X-ray diffraction. The synthesized lanthanide complexes are luminescent at room temperature and exhibit ligand- and metal-centered emission.

Studying the volatility of pyrazolone complexes of rare-earth elements by means of Knudsen effusion

The temperature dependences of the pressure of saturated vapor of pyrazolone complexes of rare-earth elements Ln(PMIP)3 (where Ln = Y, Ho, Er, Tm, Lu; PMIP = 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone) are studied via Knudsen effusion, and the enthalpy of their sublimation is determined. Mass spectra and differential scanning calorimetry data are obtained.

Synthesis of lanthanide pyrazolonate complexes by the reactions of 1-Phenyl-3-methyl-4-(2,2-dimethylpropan-1-oyl)pyrazol-5-one with metallic lanthanides. Crystal structures of [Ln(Bu t -PMP)3]2 (Ln = Gd, Tb, and Tm)

Lanthanide pyrazolonate complexes Ln(But-PMP)3 (Ln = Pr, Nd, Gd, Tb, Tm, and Lu) are synthesized by the reactions of 1-phenyl-3-methyl-4-(2,2-dimethylpropan-1-oyl)pyrazol-5-one (But-PMPH) with metallic lanthanides in the presence of catalytic amounts of the corresponding metal triiodides. The yields of the products are close to quantitative ones. The synthesized compounds can sublime in vacuo (10−3 Torr) in the temperature range from 235 to 270°C. X-ray diffraction analyses of the sublimed complexes show that they are dimers [Ln(But-PMP)3]2 (Ln = Gd, Tb, and Tm) in which metal atoms are linked by two bridging pyrazolonate fragments. The coordination environment of the lanthanide is a distorted one-capped trigonal prism.

Synthesis, structure, and catalytic properties of heteroelement carbene tungsten complexes Ph3ECH=W(OBu-t)2(OPh)2 (E = Si, Ge)

Novel silicon- and germanium-containing tungsten complexes Ph3ECH=W(OBu-t)2(OPh)2 were synthesized by the reaction of carbyne derivatives Ph3EC≡W(OBu-t)3 (E = Si, Ge) with phenol and isolated in high yields. Their structure was determined by X-ray diffraction. Individual complexes do not exhibit catalytic activity, whereas in the presence of AlBr3 they initiate metathesis polymerization of cyclooctene.