Photocatalytic decomposition of dispiro(diadamantane-1,2-dioxetane) initiated by Ce(CIO4)3 in the excited state

Photocatalytic decomposition of dispiro(diadamantane-1,2-dioxetane) (1) to adamantanone (2) initiated by Ce(ClO₄)₃ in the excited state in the MeCN−CHCl₃ (2∶1) mixture was studied. The bimolecular rate constants of quenchingk _q were determined from the kinetics of quenching of Ce^3+* by dioxetane at different temperatures. The Arrhenius parameters of the quenching were calculated from the temperature dependence ofk _q:E _a=3.2±0.3 kcal mol⁻¹ and logA=11.6±6. The quantum yields of photolysis of 1 depending on its concentration and the rate constant of the chemical reaction of Ce^3+* with 1 were determined. The latter coincides withk _q:k _ch=(2.6±0.3)·10⁹ L mol⁻¹ s⁻¹ (T=298 K). The fact that the maximum quantum yield of decomposition of dioxetane is equal to 1 indicates the absence of physical quenching of Ce^3+* with 1. Nonradiative deactivation of Ce^3+* in solutions of MeCN and in MeCN−CHCl₃ mixtures was studied. It is caused by the replacement of H₂O molecules in the nearest coordination surroundings of Ce³⁺ by solvent molecules and reversible transfer of an electron to the ligand. The activation parameters of the nonradiative deactivation of Ce^+* were determined. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 724–729, April, 1997.     

Two Novel 1-D Organic–Inorganic Composite Phosphotungstates Constructed from [Ln(α-PW11O39)2]11− Units and [Cu(en)2]2+ Bridges (Ln = CeIII/ErIII)

Abstract  Two novel organic–inorganic composite phosphotungstates, [H₉{Ce(α-PW₁₁O₃₉)₂}Cu(en)₂] · 6H₂O (1) and H₇[Cu(en)₂{Er(α-PW₁₁O₃₉)₂}Cu(en)₂] · 12H₂O (2) (en = ethylenediamine) have been synthesized by the hydrothermal reaction of the trivacant Keggin polyoxoanion [α-A-PW₉O₃₄]⁹⁻ with Ce^III or Er^III ions in the presence of Cu²⁺ ions and en, and structurally characterized by IR spectra, elemental analysis and thermogravimetric analysis. X-ray crystallographic analyses indicate that they are all built by sandwich-type [Ln(α-PW₁₁O₃₉)₂]¹¹⁻ (Ln = Ce^III, Er^III) polyoxoanions and [Cu(en)₂]²⁺ cations generating infinite one-dimensional arrangements. To our knowledge, this 1-D chain structures constituted by mono-Ln sandwiched POM units and transition-metal complex cations are very rare. Graphical Abstract  Two novel organic–inorganic composite phosphotungstates, [H₉{Ce(α-PW₁₁O₃₉)₂}Cu(en)₂] · 6H₂O (1) and H₇[Cu(en)₂{Er(α-PW₁₁O₃₉)₂}Cu(en)₂] · 12H₂O (2) (en = ethylenediamine) have been synthesized by the hydrothermal reaction of the trivacant Keggin polyoxoanion [α-A-PW₉O₃₄]⁹⁻ with Ce^III or Er^III ions in the presence of Cu²⁺ ions and en, and structurally characterized by IR spectra, elemental analysis and thermogravimetric analysis. X-ray crystallographic analyses indicate that they are all built by sandwich-type [Ln(α-PW₁₁O₃₉)₂]¹¹⁻ (Ln = Ce^III, Er^III) polyoxoanions and [Cu(en)₂]²⁺ cations generating infinite one-dimensional arrangements. To our knowledge, this 1-D chain structures constituted by mono-Ln sandwiched POM units and transition-metal complex cations are very rare.      

Chemiluminescence and catalysis of decomposition of dispiro(diadamantane-1,2-dioxetane) in solutions of lanthanide perchlorates

Chemiluminescence (CL) accompanying the decomposition of dispiro(diadamantane-1,2-dioxetane) (1) in acetonitrile solutions of Eu^III, Gd^III, Tb^III, Pr^III, and Ce^III perchlorates was studied. In the presence of Eu^III, Tb^III, and Pr^III ions, the chemiluminescence spectra contain the luminescence bands of these ions. In the cases of Gd^III and Ce^III, the chemiluminescence is caused by deactivation of singlet-excited adamantanone (2). The excitation of the lanthanide ion depends on the existence of suitable energy levels at which intracomplex excitation transfer from the³n,π^* of ketone is possible. Chemiluminescence of1 increases in solutions of Eu^III and Tb^III. The yields of CL and excitation of the lanthanide ions in the decomposition of1 in the1·Eu^III and1\Tb^III complexes were determined: φ_Eu · =0.013 ± 0.003 and φ_Tb · =0.08±0.02. The fact that the efficiency for the population of the⁵D₄-level of Tb^III is higher than that for the⁵D₁ and⁵D₀-levels of Eu^III is related to the difference in the energy gap between the triplet level of2 and the excited levels of the lanthanides. For Part I, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 730–735, April, 1997.     

XRD and UV-Vis diffuse reflectance analysis of CeO2-ZrO2 solid solutions synthesized by combustion method

A series of ceria-incorporated zirconia (Ce_1−xZr_xO₂,x = 0 to 1) solid solutions were prepared by employing the solution combustion synthesis route. The products were characterized by XRD and UV-Vis-NIR diffuse reflectance spectroscopy. The materials are crystalline in nature and the lattice parameters of the solid solution series follow Vegard’s law. Diffuse reflectance spectra of the solid solutions in the UV region show two intense bands at 250 and 297 nm which are assigned respectively to Ce³⁺ ← O²⁻and Ce⁴⁺ ← O²⁻ charge transfer transitions. The two vibrational bands in 6960 cm⁻¹ and 5168 cm⁻¹ in the NIR region indicate the presence of surface hydroxyl groups on these materials.     

Effect of non-aqueous solvents on stoichiometry and selectivity of complexes formed between 4′-nitrobenzo-15-crown-5 with Fe3+, Y3+, Cd2+, Sn4+, Ce3+ and Au3+ metal cations

The complexation processes between Fe³⁺, Y³⁺, Cd²⁺, Sn⁴⁺, Ce³⁺ and Au³⁺ metal cations with macrocyclic ligand, 4′-nitrobenzo-15-crown-5 (4′NB15C5), were studied in acetonitrile (AN), methanol (MeOH) and nitromethane (NM) solvents at different temperatures using conductometric method. The conductance data show that the stoichiometry of the complexes formed between this macrocyclic ligand and Cd²⁺, Au³⁺ cations is 1: 1 (ML), but in the case of Fe³⁺, Y³⁺ and Ce³⁺ metal cations, 2: 1 (M₂: L) and 2: 2 [M₂: L₂] complexes are formed in nitromethane solutions. The results show, that the selectivity of 4’NB15C5 for the studied metal cations in methanol solutions at 15°C is: Sn⁴⁺ > Cd²⁺ > Y³⁺ > Fe³⁺ ∼ Ce³⁺ > Au³⁺, but in the case of acetonitrile, the stability order was found to be: Y³⁺ > Au³⁺ > Fe³⁺ > Cd²⁺. The values of stability constants of the 1: 1 [M: L] complexes were determined from conductometric data using a GENPLOT computer program. The values of thermodynamic parameter (ΔH _c ^o and ΔH _c ^o) for formation of the complexes were obtained from temperature dependence of the stability constants, using the van’t Hoff plots. The results show that the values of standard enthalpy (ΔH _c ^o) and standard entropy (ΔH _c ^o) change with the nature of the non aqueous solvents.     

Chemiluminescence in the reaction of the RuII trisbipyridyl complex with dimethyldioxirane

The reaction of dimethyldioxirane (1) with the Ru^II trisbipyridyl complex accompanied by chemiluminescence (CL) was studied. It is established that the intensity of CL and the rate of its decay increase proportionally with the concentration of Ru^II. The bimolecular rate constant (k ₂) of the reaction of1 with Ru^II was determined. The activation parameters (E _a and logA) for this reaction were calculated from the temperature dependence ofk ₂. The excitation yield of Ru^II* (η _Ru ^* ) was estimated. The quenching of Ru^II* by dioxirane was studied, and the bimolecular quenching constant and the coefficient of excitation regeneration were determined. It was suggested that the catalysis of the decomposition of1 and the excitation of Ru^II occurvia a mechanism of chemically initiated electron exchange. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1138–1142, June, 1997.     

(N-benzoyl)trichloroacetimidoylphosphonate

A method for the synthesis ofO,O-diethyl (N-benzoyl)trichloroacetimidoylphosphonate (1) by successive reaction ofN-(1-diethoxyphosphoryl-2,2-dichlorovinyl)benzamide with Me₃SiCl and Cl₂ was proposed. The reaction of phosphonate1 with R₃P follows the [4+1] cycloaddition mechanism to give phosphoranes, whose stability and further transformations are controlled by the nature of R. Dedicated to the memory of Academician M. I. Kabachnik on his 90th birthday. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2101–2104, October, 1998.     

Master sintering curve for Gd-doped CeO<Subscript>2</Subscript> solid electrolytes

The sintering behavior of gadolinia-doped ceria powders was studied by the master sintering curve (MSC). Dilatometric analyses of powders produced by a soft chemical method were performed to provide the experimental data set for the construction of the MSC. The assumed model provided good fittings of the MSC and the activation energy for the sintering of Ce_1−x Gd _x O_3−δ, with x = 0, 0.05, 0.1, and 0.2 were found to be in the 218–325 KJ/mol range, depending on the dopant content. The results supported that both the nanometric size of the particles and the difference in ionic radii between Gd³⁺ and Ce⁴⁺ affects the sintering of Gd-doped CeO₂.     

Synthesis of corundum doped with cerium in supercritical water fluid

The properties of fine crystalline corundum doped with cerium (α-Al₂O₃: Ce³⁺) during synthesis in a supercritical fluid have been studied. The synthesis of corundum has been carried out by the thermal treatment of hydrargillite, Al(OH)₃, at T = 415°C and {ie290-1} MPa in reaction media that contained from 0.001 to 0.25 wt % of cerium. Cerium ions are incorporated into the boehmite lattice during the transformation of hydrargillite into boehmite, which forms fine monocrystals of the doped corundum with a size from 20 to 50 μm. The size of the corundum crystals increases with increasing pressure and increasing concentration of cerium. The synthesized α-Al₂O₃: Ce³⁺ reveals a luminescent band in the UV region at 352 nm and a blue band at 421 nm. The intensity of the cerium ion luminescence in corundum increases with an increase in the water fluid pressure during synthesis. The follow-up annealing of α-Al₂O₃: Ce³⁺ at 1400°C in a vacuum leads to a decrease in the luminescence. It has been concluded that spectrally active complex structures that include cerium ions, oxygen vacancies, and hydroxyl groups are produced in the media of a supercritical water fluid upon the synthesis of boehmite and corundum. Exposure to high temperatures causes their transformation.     

The reaction of diaryl derivatives of bis(triphenylphosphine)platinum(II) with [60]fullerene as a route to the platinum complex η2-C60Pt(PPh3)2

The reaction ofcis-Ar₂Pt(PPh₃)₂ (Ar=p-MeC₆H₄ (1a) and Ar=Ph (1b)) with [60]fullerene in toluene afforded the metal-fullerene complex η²-C₆₀Pt(PPh₃)₂ (2), which was isolated in the crystalline state. The reductive elimination between C₆₀ and1a or1b also resulted in the formation of biaryls (p-MeC₆H₄)₂ and Ph−Ph. The composition and structure of the compounds were established by¹H and³¹P NMR spectroscopy, electronic absorption spectroscopy, and elemental analysis. The homolytic phosphorylation of2 was additionally studied by the ESR method.     

Blue and green centers in natural apatites by ERS and optical spectroscopy data

Using ESR and optical spectroscopy we showed that the blue coloring is imparted to natural apatites by SO ₃ ⁻ radicals and the green coloring is due to SiO ₃ ⁻ radicals complexed with rare earth ions, SiO ₃ ⁻ -(Ce³⁺+K). The role of U⁴⁺ and Th⁴⁺ isomorphous actinide ions in the process of color center formation is investigated. United Institute of Geology, Geophysics, and Mineralogy, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Struktumoi Khimii, Vol. 36, No. 1, pp. 89–101, January–February, 1995. Translated by L. Smolina     

Synthesis, structure, and properties of a binuclear Fe(III) complex with N-(1-propanol)-N,N-bis(3-tert-butyl-5-methyl-2-hydroxybenxyl)amine

Mannich reaction of 2-Amino propanol, 2-tert-butyl-4-methylphenol, and formaldehyde in the ratio of 1:2:2 provides a new compound, N-(1-propanol)-N,N-bis(3-tert-butyl-5-methyl-2-hydroxybenxyl)amine (H₃L), which has been characterized by X-ray crystallography and elemental analysis. In the presence of Et₃N, the reaction of H₃L and FeCl₃·6H₂O gives a dinuclear Fe(III) complex [Fe₂L₂] 1, which has been characterized by X-ray crystallography, magnetic measurement, and cyclic voltammetry. The value of μ_eff at room temperature (5.97 μ_B) is much less than the expected spin-only value (8.37 μ_B) of two high spin (hs) Fe³⁺ (S = 5/2) ions [μ = g[∑ZS(S + 1)]^1/2], indicating there are strong coupling interactions between Fe³⁺ ions. The magnetic behavior of 1 denotes the occurrence of intramolecular antiferromagnetic interactions (J = −13.35 cm⁻¹ ). CV of 1 reveals two reversible waves at 0.433 and 1.227 V versus AgCl/Ag, which can be ascribed to the successive redox coupling of Fe^IIFe^II/Fe^IIIFe^II and Fe^IIIFe^II/Fe^IIIFe^III, respectively.     

Silicotungstic acid modified Ce‐Fe‐Ox catalyst for selective catalytic reduction of NOx with NH3: Effect of the amount of HSiW

The HSiW(x)/Ce‐Fe catalysts were used to research the effect of silicotungstic acid contents on the catalytic activity in the selective catalytic reduction of NO_x with NH₃. Doping different contents of silicotungstic acid affected surface species and redox property as well as the catalytic activity. With the increasing amount of HSiW (x = 5%, 10% and 20%), the redox reaction between Fe³⁺/Fe²⁺ and Ce⁴⁺/Ce³⁺ enhanced, which could improve the ratio of Ce³⁺ and Fe³⁺. And then, more Ce³⁺ increased the ratio of chemisorbed oxygen (O_α). Besides, the type and strength of acid sites over HSiW(_x)/Ce‐Fe was affected by the HSiW contents. These factors facilitated the catalytic performance. Thus, the NO_x conversion of HSiW(x)/Ce‐Fe(x = 20%) was higher than 90%, which maintained in a wide temperature range between 200 and 400 °C.     

Chemie der Seltenerdmetalle, 19. Mitt.: Dissoziation des Ce(III)-succinats im sauren Gebiet

Zusammenfassung Die Dissoziation von Ce₂ Suc ₃·3 H₂O^** in Perchlorsäure-Lösungen wurde verfolgt und die Dissoziationskonstanten der Succinationen: (CeSuc)⁺ und (CeSuc ₂)^– unter Benützung einer Löslichkeitsmethode in 1m-NH₄ClO₄-Lösung bei 25°C bestimmt. Die Löslichkeitsprodukte von Ce₂ Suc ₃: [Ce³⁺]²[Suc ^2–]³, [CeSuc ⁺]²[Suc ^2–], [CeSuc ⁺][CeSuc ₂ ^–] wurden bestimmt.

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The dissociation of Ce₂ Suc ₃·3H₂O in perchloric acid solutions was investigated. The dissociation constants of the succinate ions (CeSuc)⁺ and (CeSuc ₂)^– were determined inM-NH₄ClO₄ at 25° using a solubility method and the solubility products of Ce₂ Suc ₃, i. e. [Ce³⁺]²[Suc ^2–]³, [CeSuc ⁺]²[Suc ^2–], [CeSuc ⁺][CeSuc ₂ ^–] measured.

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18. Mitt.:R. Pastorek, Lanthantartrate im neutralen und alkal. Bereich. Mh. Chem.99, 676 (1968).     

Hypercoordinated gold (i) compounds

The reaction of [O(AuPPh₃)₃]⁺BF₄ ⁻ with a Li, K derivative ofo-cresol followed by the interaction of the reaction product with CO₂ gave (triphenylphosphine)gold acetate. The reaction of ClAuPPh₃ witho-LiC₆H₄SLi afforded (triphenylphosphine)gold thiophenoxide. According to the data of X-ray structural analysis, the latter occurs as a dimer formed through an intermolecular secondary Au…Au bond. The reaction of this complex with diazomethane was accompanied by insertion of carbene into the Au−S bond to form a new gold complex, PhSCH₂AuPPh₃. The reactions with PPh₃Au⁺BF₄ ⁻ or HBF₄ yielded a new tetranuclear gold thiocluster, {[PhS(AuPPh₃)₂]²⁺(BF₄ ⁻)}₂, which involves Au…Au bonds that differ in strength. The structures of the compounds obtained were established by X-ray structural analysis¹H and³¹P NMR spectroscopy, and FAB mass spectrometry. For Part 4, seeIzv. Akad. Nauk, Ser. Khim., 1997, 2244 [Russ. Chem. Bull., 1997,46 2127 (Engl. Transl)]. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 350–355, February, 1998.     

Assembly of a Supramolecular Architecture Based on Keggin POMs and Lanthanide Coordination Cations

Two new compounds based on Keggin polyoxometalates (POMs) [SiW₁₂O₄₀]⁴⁻ (SiW₁₂), [Na(H₂O)₃(H₂L)SiW₁₂O₄₀](H₂L)₂   6H₂O (1), and [Ce(H₂O)₃(HL)₂(H₂L)]₂[SiW₁₂O₄₀]₂ 10H₂O (2) (HL = C₆H₅NO₂ = isonicotinic acid), have been conventionally synthesized and characterized by routine methods. Compound 1 possesses a 1D right-handed helical structure constructed by SiW₁₂O₄₀ ⁴⁻ {SiW₁₂} and [Na(H₂O)₃(HL)] complexes. Interestingly, these right-handed helical chains are linked together via H-bonds forming a novel chiral layer. By using the similar synthesis method to that for compound 1, except for employing Ce³⁺ cations in instead of La³⁺ cations, a 3D supramolecular compound 2 based on SiW₁₂ and Ce³⁺ coordination cations has been obtained, which contains 1D channels along a axis. Additionally, the luminescence properties of 2 were studied. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis, properties, and reactivity of the stilbene complex of ytterbium (PhCH=CHPh)Yb(THF)2. Crystal structure of (2,4,6-But 3C6H2O)2Yb(THF)3

The stilbene complex of ytterbium (PhCH=CHPh)Yb(THF)₂ (1) was prepared by the reaction of YbI₂(THF)₂ with a twofold excess of (PhCH=CHPh)⁻ Li⁺. Based on the data of IR and ESR spectroscopy and on the results of magnetic measurements, compound1 was characterized as a complex of divalent ytterbium with the stilbene dianion. The reactivity of complex1 toward different types of reagents was studied. The structure of the product of the reaction of1 with 2,4,6-tri(tert-butyl)phenol (2,4,6-Bu^t ₃C₆H₂O)₂Yb(THF)₃ was established by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2345–2350, November, 1998.     

Highly Dispersed Ce x Zr1−x O2 Nano-Oxides Over Alumina, Silica and Titania Supports for Catalytic Applications

We have been exploring the utilization of supported ceria and ceria–zirconia nano-oxides for different catalytic applications. In this comprehensive investigation, a series of Ce _x Zr_1−x O₂/Al₂O₃, Ce _x Zr_1−x O₂/SiO₂ and Ce _x Zr_1−x O₂/TiO₂ composite oxide catalysts were synthesized and subjected to thermal treatments from 773 to 1073 K to examine the influence of support on thermal stability, textural properties and catalytic activity of the ceria–zirconia solid solutions. The physicochemical characterization studies were performed using X-ray diffraction (XRD), Raman spectroscopy (RS), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HREM), thermogravimetry and BET surface area methods. To evaluate the catalytic properties, oxygen storage/release capacity (OSC) and CO oxidation activity measurements were carried out. The XRD analyses revealed the formation of Ce_0.75Zr_0.25O₂, Ce_0.6Zr_0.4O₂, Ce_0.16Zr_0.84O₂ and Ce_0.5Zr_0.5O₂ phases depending on the nature of support and calcination temperature employed. Raman spectroscopy measurements in corroboration with XRD results suggested enrichment of zirconium in the Ce _x Zr_1−x O₂ solid solutions with increasing calcination temperature thereby resulting in the formation of oxygen vacancies, lattice defects and oxygen ion displacement from the ideal cubic lattice positions. The HREM results indicated a well-dispersed cubic Ce _x Zr_1−x O₂ phase of the size around 5 nm over all supports at 773 K and there was no appreciable increase in the size after treatment at 1073 K. The XPS studies revealed the presence of cerium in both Ce⁴⁺ and Ce³⁺ oxidation states in different proportions depending on the nature of support and the treatment temperature applied. All characterization techniques indicated absence of pure ZrO₂ and crystalline inactive phases between Ce–Al, Ce–Si and Ce–Ti oxides. Among the three supports employed, silica was found to stabilize more effectively the nanosized Ce _x Zr_1−x O₂ oxides by retarding the sintering phenomenon during high temperature treatments, followed by alumina and titania. Interestingly, the alumina supported samples exhibited highest OSC and CO oxidation activity followed by titania and silica. Details of these findings are consolidated in this review.     

Thermodynamics of mixed-ligand complexation of cerium group lanthanide ethylenediaminetetraacetates

The thermodynamic parameters (logK, Δ _r G ⁰, Δ _r H, and Δ _r S) for mixed-ligand complexation of LnEdta⁻ (Ln³⁺ = La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Gd³⁺) with iminodiacetate and nitrilotriacetate ions in aqueous solution at 298.15 K and ionic strength I = 0.5 (KNO₃) were determined by calorimetry and pH-metry. The variation of the thermodynamic parameters of the reactions over the lanthanide series was discussed.     

Synthesis and photoinduced isomerization ofansa{·5,·5′-[1,1′-(1-silacyclopent-3-ene-1,1-diyl)bis(indenyl)]} dichlorozirconium The crystal structure of itsmeso form

ansa{·⁵,·⁵′-[1,1′-(1-silacyclopent-3-ene-1,1-diyl)bis(indenyl)]} dichlorozirconium (1a,b) was synthesized. The crystal structure ofmeso-[(1,4-CH₂CH=CHCH₂)Si(C₉H₆)₂ZrCl₂] (1b) was established by X-ray diffraction analysis. Photoinduced interconversion of the racemic (1a) andmeso forms was studied under various conditions. The photostationary state (rac: meso=55∶45) was established rapidly when solutions ofansa-zirconocene were irradiated with visible light. Deceased Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2351–2356, November, 1998.