S 98 Synthesis of cyclometallated platinum complexes with substituted thienylpyridines and detailed characterization of their luminescence properties [Text] / D. N. Kozhevnikov, V. N. Kozhevnikov, M. M. Ustinova, A. Santoro, D. W. Bruce, B. Koenig, T. Fisher, M. Zabel, H. Yersin // Inorganic Chemistry . - 2009. - Vol. 48, № 9. - P4179-4189 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Synthesis of various derivatives of 2-(2-thienyl)pyridine via substituted 3-thienyl-1,2,4-triazines is reported. The final step of the synthesis is a transformation of the triazine ring to pyridine in an aza-Diels-Alder-type reaction. The resulting 5-aryl-2-(2-thienyl)pyridines (HL1-HL4) and 5-aryl-2-(2-thienyl)cyclopenteno[c]pyridines (HL5-HL8) (with aryl = phenyl, 4-methoxyphenyl, 2-naphtyl, and 2-thienyl) were used as cyclometallating ligands to prepare a series of eight luminescent platinum complexes of the type [Pt(L)(acac)] (L = cyclometallating ligand, acac = acetylacetonato). X-ray single crystal structures of three complexes of that series, [Pt(L5)(acac)] = [Pt(5-phenyl- 2-(2-thienyl)cyclopenteno[c]pyridine)(acac)], [Pt(L6)(acac)] = [Pt(5-(4-methoxy)-2-(2-thienyl)cyclopenteno[c]py- ridine)(acac)], and [Pt(L7)(acac)] = [Pt(5-(2-naphtyl)-2-(2-thienyl) cyclopenteno[c]pyridine)(acac)] were determined. Photoluminescence and electronic absorption spectra of the new [Pt(L)(acac)] complexes are reported. For two representative compounds of that series, [Pt(L4)(acac)] and [Pt(L5)(acac)], a detailed photophysical characterization based on highly resolved emission and excitation spectra, as well as on emission decay properties, was carried out. The studies down to low temperature (T = 1.2 K) and up to high magnetic fields (6 = 10 T) allowed us to characterize the three individual substates of the emitting triplet state. In particular, it is shown that the lowest triplet states of [Pt(L4)(acac)] and [Pt(L5)(acac)] are largely ligand-centered (LC) of3jtjt*character, which experience only weak spin- orbit couplings to higher lying singlet states |
S 45 Selective sorption of gold (III), platinum (IV) and palladium (II) [] : доклад, тезисы доклада / S. Yu. Bratskaya, A. V. Pestov, A. Slobodyuk, V. A. Avramenko, Yu. G. Yatluk // EUCHIS 2009 - 9th International Conference of the European Chitin Society , Venice, Italy, 23-26 May 2009 : conference book. - Venice, Italy, 2009. - 146 (P03-13) Рубрики: ХИМИЧЕСКИЕ НАУКИ |
Т 42 Тиокарбамоилхитозан - селективный сорбент ионов платины (II) и палладия(II) [] = Thiocarbamoylchitosan - selective sorbent of ions of platinum (IV) and palladium : доклад, тезисы доклада / А. В. Пестов, С. Ю. Братская, А. Б. Слободюк, В. А. Авраменко, Ю. Г. Ятлук // Современные перспективы в исследовании хитина и хитозана : материалы IX Международной конф., Ставрополь, 13-17 окт. 2008 г. : докл. - Ставрополь, 2008. - С. 85-87. - Библиогр.: с. 87 (6 назв.) Рубрики: ХИМИЧЕСКИЕ НАУКИ |
P 51 Petrological model of formation of giant ore deposits [Text] / A. A. Marakushev, N. A. Paneyakh, V. L. Rusinov, N. N. Pertsev, I. A. Zotov // Geology of Ore Deposits. - 1998. - Vol. 40, № 3. - P211-227. - Bibliogr. : p. 227 (46 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): PETROLOGICAL MODEL -- MODELLING -- ORE -- ORE DEPOSITS Аннотация: The available data on the giant ore deposits of chromium (Kempirsai in the Urals), platinum-group metals (Bushveld in Africa), platinum-bearing copper-nickel ores (Talnakh in the Noril'sk district, northern part of the Siberian Platform), zinc-copper (massive sulfide) ores (Gai, Sibai, and Uchaly) and apatite deposits (Khibiny, the Kola Peninsula) is summarized. The giant sizes of the deposits are caused by extraordinary ore-forming processes directly associated with the highly extensive petrogenetic processes. These processes resulted in the formation of peculiar dunites in the hyperbasite complexes (chromite ores), agpaitic urtites in alkaline associations (apatite deposits), development of low-sulfide horizons and hortonolite dunites in the basite-hyperbasite layered intrusions (platinum-group metal deposits), specific processes of transmagmatic sulfurization of the iron-rich igneous differentiates (Cu-Ni sulfide and massif sulfide ores), and processes of magmatic replacement of hyperbasites that cause the alkaline agpaitic affinity of magmatism. This agpaitic tendency increases the solubility of carbon-bearing fluid components (CO2, CH4, etc.) in magma and leads to the concentration of ore metals, which form chloride-carbonate and hydrocarbon migrating compounds in the transmagmatic fluids. Some mineralogical-petrological prospecting criteria are deduced on the basis of genetic models of giant ore deposits. |
N 10 N-(2-(2-Pyridyl)ethyl)chitosan (PEC) for Pd(II) and Pt(IV) sorption from HCl solutions [] / L. A. Santos Sorena, M. Ruiz, A. V. Pestov, A. M. Sastre, Yu. G. Yatluk, E. Guibal // Cellulose. - 2010. - 6 December. - Online first : рис., табл. Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Chitosan was modified by grafting 2-pyridyl-ethyl moieties on the biopolymer backbone for the synthesis of a Platinum Group Metal (PGM) sorbent. The sorbent was tested for Pd(II) and Pt(IV) sorption from HCl solutions. Stable for HCl concentrations below 0.5 M, the sorbent reached sorption capacities as high as 3.2 and 2.6 mmol metal g1 for Pd(II) and Pt(IV), respectively. Metal sorption mainly proceeds by electrostatic attraction in acidic solutions, though a contribution of complexation mechanism cannot be totally rejected. The resistance to intraparticle diffusion is the main controlling mechanism for uptake kinetics. While agitation speed has a limited effect on kinetics, metal concentration and sorbent dosage have a greater effect on the kinetic profiles. The intraparticle diffusivity varies between 3 10?11 and 4.5 1010 m2 min1. Thiourea (combined with HCl solution) is used for Pd(II) and Pt(IV) desorption. The resin could be desorbed and recycled for a minimum of five cycles maintaining high efficiencies of sorption and desorption |
T 45 Thiocarbamoyl chitosan as a novel sorbent with high sorption capacity and selectivity for the ions of gold(III), platinum(IV), and palladium [Electronic resource] / A. V. Pestov, S. Yu. Bratskaya, A. Slobodyuk, V. A. Avramenko, Yu. G. Yatluk // Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya). - 2010. - Vol. 59, № 7. - P1303-1306 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): CHITOSAN -- THIOCARBAMOYL CHITOSAN -- IONS OF GOLD(III) Аннотация: Thiocarbamoyl chitosan (TCC) was synthesized by grafting thiourea on chitosan backbone in eutectic composition of ammonium thiocyanate—thiourea. Insoluble products with the amno group functionalization degree of 0.3–1.1 can be prepared by varying the conditions of polymer-analogous (synthesis in a gel) transformation. Structure of the synthesized chitosan derivatives was characterized by elemental analysis, diffuse reflectance infrared spectroscopy, and the solid state 13C NMR. Study of sorption properties of TCC shows high sorption capacity and selectivity for the ions of gold(III), platinum(IV), and palladium(II) as evidenced by results obtained at pH 2 in the presence of 100–1000-fold excess of iron(III), copper(II), zinc(II), and nickel(II). Sorption capacity of TCC for all ions increases with the increase in the degree of substitution and changes in the series: AuIII > PdII > PtIV \\\\Expert2\\nbo\\Russian Chemical Bulletin\\2010, 59 (7), 1303-1306.pdf |
P 17 Palladium and platinum sorption on a thiocarbamoyl-derivative of chitosan [Text] / A. Butewicz, K. Campos Galivan, A. V. Pestov, Yu. G. Yatluk, A. W. Trochimczuk, E. Guibal // Journal of Applied Polymer Science . - 2010. - Vol. 116, № 6. - P3318-3330 : рис. Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Immobilizing thiourea onto chitosan allowed using the polymer for the recovery of platinum groups metals (PGMs) in acidic solutions (up to 1–2M HCl concentrations). At low HCl concentration protonated amine groups may sorb chloroanionic metal species (electrostatic attraction mechanism); however, most of sorption proceeds through chelation on sulfur containing groups (less sensitive to acidic conditions). The bi-site Langmuir equation was used for fitting sorption isotherms. The sorption of PGMs was weakly affected by the composition of the solution (presence of high concentration of anions and base metals). Maximum sorption capacities for Pd(II) and Pt(IV) ranged between 274 and 330 mg g?1 in 0.25M HCl solutions and decreased to 150–198 mg g?1 in 2M HCl solutions: Pd(II) sorption was systematically higher than Pt(IV) sorption. The pseudo-second rate equation was used for modeling the uptake kinetics. Agitation speed hardly affected uptake kinetics indicating that external diffusion resistance is not the rate controlling step. Desorption yield higher than 85% were obtained using thiourea in 0.1M HCl solution. The adsorbents could be reused for at least three cycles |
N 10 N-(2-(2-Pyridyl)ethyl)chitosan (PEC) for Pd(II) and Pt(IV) sorption from HCl solutions [Text] / L. A. Santos Sorena, M. Ruiz, A. V. Pestov, A. M. Sastre, Yu. G. Yatluk, E. Guibal // Cellulose. - 2011. - Vol. 18, № 2. - P309-325. - Bibliogr. : p. 324-325 (32 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Chitosan was modified by grafting 2-pyridyl-ethyl moieties on the biopolymer backbone for the synthesis of a Platinum Group Metal (PGM) sorbent. The sorbent was tested for Pd(II) and Pt(IV) sorption from HCl solutions. Stable for HCl concentrations below 0.5 M, the sorbent reached sorption capacities as high as 3.2 and 2.6 mmol metal g?1 for Pd(II) and Pt(IV), respectively. Metal sorption mainly proceeds by electrostatic attraction in acidic solutions, though a contribution of complexation mechanism cannot be totally rejected. The resistance to intraparticle diffusion is the main controlling mechanism for uptake kinetics. While agitation speed has a limited effect on kinetics, metal concentration and sorbent dosage have a greater effect on the kinetic profiles. The intraparticle diffusivity varies between 3 ? 10?11 and 4.5 ? 10?10 m2 min?1. Thiourea (combined with HCl solution) is used for Pd(II) and Pt(IV) desorption. The resin could be desorbed and recycled for a minimum of five cycles maintaining high efficiencies of sorption and desorption \\\\Expert2\\nbo\\Cellulose\\2011, v.18, p. 309.pdf |
T 45 Thiocarbamoyl chitosan: Synthesis, characterization and sorption of Au(III), Pt(IV), and Pd(II) [Text] / S. YU. Bratskaya, A. Yu. Ustinov, Yu. A. Azarova, A. V. Pestov // Carbohydrate Polymers. - 2011. - Vol. 85, № 4. - P854-861 : ил. - Bibliogr. : p. 860-861 (39 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Here we suggest a new method of chitosan sulfur derivatives (thiocarbamoylchitosans, TC-chitosans) synthesis via reaction in eutectic two-component system ammonium rodanide–thiourea that allows significant increase of substitution degrees at the reduced time and reagent consumption as compared to conventional synthetic procedures. The sorption properties of TC-chitosans with substitution degrees (DS) from 0.4 to 0.9 toward Au(III), Pt(IV), Pd(II) ions were studied in chloride solutions, including systems with 10 to 1000-fold excess of Fe(III), Cu(II), and Zn(II) over the precious metal ions content. The sorption capacities of TC-chitosans increase with DS and change in the row: Au(III) Pd(II) Pt(IV) ? Cu(II) Fe(III) Zn(II). The maximum sorption capacities of TC-chitosan with DS 0.9 for Pt(IV), Pd(II), and Au(III) were 1.24 mmol/g, 3.43 mmol/g, and 3.81 mmol/g, respectively. Characterization of precious metals oxidation states by the XPS method after the sorption on TC-chitosan revealed that the platinum and gold recovery occurred with reduction of Au(III) to Au(I)/Au(0) and Pt(IV) to Pt(II)???? \\\\Expert2\\nbo\\Carbohydrate Polymers\\2011, v. 85, p.854.pdf |
2,2 '-Bipyridinyl carboranes as B,N,N-ligands in cyclometallated complexes of platinum(II) [] / A. M. Prokhorov, P. A. Slepukhin, V. L. Rusinov, V. N. Kalinin, D. N. Kozhevnikov // Chemical Communications. - 2011. - Vol. 47, № 27. - С. 7713-7715 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): O-CARBORANE -- METALLACARBORANES -- PHOTOLUMINESCENT Аннотация: Novel B,N,N-cyclometallated Pt(II) complexes of 2,2'-bipyridin-6-yl carboranes exhibit absorption and emission similar to relative Pt(II) complexes of aromatic C,N,N-ligands: the same transitions but lower intensities. DFT calculations suggest the former emits from the (3)MLCT state while for the latter the mixed (3)ICT-MLCT transitions should be considered \\\\expert2\\NBO\\Chemical Communications\\2011,v.47. p.7713.pdf |
N 10 N-(2-(2-Pyridyl)ethyl)chitosan (PEC) for Pd(II) and Pt(IV) sorption from HCl solutions / L. A. Santos Sorena, M. Ruiz, A. V. Pestov, A. M. Sastre, Yu. G. Yatluk, E. Guibal // Cellulose. - 2011. - Vol. 18, № 2. - С. 309-325 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): CHITOSAN – PYRIDYL GROUPS -- PALLADIUM -- PLATINUM Аннотация: Chitosan was modified by grafting 2-pyridyl-ethyl moieties on the biopolymer backbone for the synthesis of a Platinum Group Metal (PGM) sorbent. The sorbent was tested for Pd(II) and Pt(IV) sorption from HCl solutions. Stable for HCl concentrations below 0.5 M, the sorbent reached sorption capacities as high as 3.2 and 2.6 mmol metal g?1 for Pd(II) and Pt(IV), respectively. Metal sorption mainly proceeds by electrostatic attraction in acidic solutions, though a contribution of complexation mechanism cannot be totally rejected. The resistance to intraparticle diffusion is the main controlling mechanism for uptake kinetics. While agitation speed has a limited effect on kinetics, metal concentration and sorbent dosage have a greater effect on the kinetic profiles. The intraparticle diffusivity varies between 3 ? 10?11 and 4.5 10?10 m2 min?1. Thiourea (combined with HCl solution) is used for Pd(II) and Pt(IV) desorption. The resin could be desorbed and recycled for a minimum of five cycles maintaining high efficiencies of sorption and desorption. ?? |
P 58 Phosphorescence vs Fluorescence in Cyclometalated Platinum(II) and Iridium(III) Complexes of (Oligo)thienylpyridines / D. N. Kozhevnikov, V. N. Kozhevnikov, M. Z. Shafikov, A. M. Prokhorov, D. W. Bruce, J. A. Gareth Williams // Inorganic Chemistry . - 2011. - Vol. 50, № 8. - С. 3804-3815 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): OLIGOTHIENYLPYRIDINES -- LIGANDS -- LUMINESCENCE PROPERTIES Аннотация: Two newly prepared oligothienylpyridines, 5-(2-pyridyl)-5?-dodecyl-2,2?-bithiophene, HL2, and 5-(2-pyridyl)-5??-dodecyl-2,2?:5?,2??-ter-thiophene, HL3, bind to platinum(II) and iridium(III) as NC-coordinating ligands, cyclometallating at position C4 in the thiophene ring adjacent to the pyridine, leaving a chain of either one or two pendent thiophenes. The synthesis of complexes of the form [PtLn(acac)] and [Ir(Ln)2(acac)] (n = 2 or 3) is described. The absorption and luminescence properties of these four new complexes are compared with the behavior of the known complexes [PtL1(acac)] and [Ir(L1)2(acac)] {HL1 = 2-(2-thienyl)pyridine}, and the profound differences in behavior are interpreted with the aid of time-dependent density functional theory (TD-DFT) calculations. Whereas [PtL1(acac)] displays solely intense phosphorescence from a triplet state of mixed ??*/MLCT character, the phosphorescence of [PtL2(acac)] and [PtL3(acac)] is weak, strongly red shifted, and accompanied by higher-energy fluorescence. TD-DFT reveals that this difference is probably due to the metal character in the lowest-energy excited states being strongly attenuated upon introduction of the additional thienyl rings, such that the spin?orbit coupling effect of the metal in promoting intersystem crossing is reduced. A similar pattern of behavior is observed for the iridium complexes, except that the changeover to dual emission is delayed to the terthiophene complex [Ir(L3)2(acac)], reflecting the higher degree of metal character in the frontier orbitals of the iridium complexes than their platinum counterparts.?? \\\\Expert2\\nbo\\Inorganic Chemistry\\2011, v.50, p.3804.pdf |
T 44 Thermal stability of new sorption materials based on polysiloxanes / L. K. Neudachina, A. Y. Golub, E. M. Gorbunova, Yu. G. Yatluk // Glass Physics and Chemistry. - 2011. - Vol.37, №6. - С. 603-612 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): THERMAL STABILITY -- THIOCARBAMOYLATED POLYSILOXANES -- SILOXANE MATRIX Аннотация: The thermal stability of the unmodified, aminated, and thiocarbamoylated polysiloxanes has been studied. The siloxane matrix is stable in the temperature range up to 800°C. For the first time, mass spectrometry has been applied to the analysis of the composition of the gaseous products of thermal decomposition of the studied polysiloxanes. It has been shown that, in the process of thermal decomposition, the terminal functional groups are detached and oxidized. Water, ammonia, nitrogen, carbon, and sulfur (in the case of thiourea-modified sorbent) oxides are formed predominantly. The quantitative removal of functional groups during heating up to 800°C has been confirmed by IR spectroscopy. A mechanism of thermal decomposition of polysiloxane xerogels has been proposed. It has been found that adsorption of platinum increases the thermal stability of the samples \\\\Expert2\\nbo\\Glass Physics and Chemistry\\2011, V. 37, N 6, P.603-612.pdf |
C 98 Cyclometallated Pt-II complexes of 2-(2-thienyl)-4-(cycloalkylimino)-substituted quinazolines [Electronic resource] / E. V. Nosova, T. N. Moshkina, D. S. Kopchuk, G. N. Lipunova, P. A. Slepukhin, V. N. Charushin // Mendeleev Communications. - 2016. - Vol. 26, № 2. - С. 129-130 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): PLATINUM COMPLEXES -- DIODES Аннотация: The title complexes were prepared based on 2-(thiophen-2-yl)-4-(morpholin-4-yl)- and 2-(thiophen-2-yl)-4-(piperidin-1-yl)-substituted quinazolines and found to exhibit luminescent properties \\\\expert2\\NBO\\Mendeleev Communications\\2016, v.26, p. 129-130.pdf |
F 33 Features of sorption preconcentration of noble metal ions with sulfoethylated amino polymers / L. M. Alifkhanova, K. Y. Lopunova, A. A. Marchuk [и др.] // Russian journal of inorganic chemistry. - 2021. - Vol. 66, № 6. - С. 909-915 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Dependencies for the sorption of palladium(II), gold(III), and platinum(IV) chloro complexes from individual and binary solutions with sorbents based on sulfoethylated polyallylamine and poly(aminostyrene) have been obtained. It has been found that predominant sorption mechanism is complexation with functional groups of the sorbents for gold(III) and palladium(II) and ion exchange for platinum(IV). It has been shown that increase in the sulfoethylation degree of aminopolymer matrix leads to decrease of platinum(IV) sorption and therefore, to increase in palladium(II) sorption selectivity relative to this ion. This effect is the largest for the sorbents based on polyallylamine. The conditions of quantitative desorption of the studied metals from sorbent surface have been determined. The sorption of gold(III) by the sorbent based on polyallylamine has been shown to be complicated by gold(III) reduction in sorbent phase. |
Effect of the degree of sulfoethylation of polyethylenimine on the selectivity of sorption of palladium(II) from binary solutions / E. I. Kapitanova, A. R. Sinelshchikova, Yu. S. Petrova [et al.] // Russian chemical bulletin. - 2021. - Vol. 70, № 6. - P1161-1166 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): POLYETHYLENIMINE -- SULFOETHYLATION -- SORPTION -- PLATINUM(IV) -- PALLADIUM(II) -- GOLD(III) |
Platinum(II) acetylacetonate complex based on 5-(3-aminophenyl)-2-(2-thienyl)pyridine: synthesis, crystal structure, and photophysical properties / D. S. Kopchuk, P. A. Slepukhin, O. S. Taniya [et al.] // Russian Journal of Coordination Chemistry. - 2022. - Vol. 48, № 7. - P430-435 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: The Pt(II) acetylacetonate complex [(L)Pt(Acac)] based on aminophenyl-substituted 2-(2-thienyl)pyridine (L) was synthesized, its photophysical properties were studied and compared with these properties for a similar complex containing no amino group in the ligand. The structure of the complex was confirmed by X-ray diffraction (CIF file CCDC no. 2144689), 1H and 13C NMR spectroscopy, ESI mass spectrometry, and elemental analysis. |