Silicate complexation of NpO<Subscript>2</Subscript><Superscript>+</Superscript> ion in perchlorate media

Complexation behavior of NpO₂ ⁺ with ortho-silicic acid (o-SA) has been studied using solvent extraction at ionic strengths varying from 0.10 to 1.00M (NaClO₄) at pcH 3.68±0.08 and 25 °C with bis-(2-ethylhexyl) phosphoric acid (HDEHP) as the extractant. The stability constant value (log β₁) for the 1:1 complex, NpO₂(OSi(OH)₃), was found to decrease with increase in ionic strength of the aqueous phase [6.83±0.01 at I=0.10M to 6.51±0.02 at I = 1.00M]. These values have been fitted in the SIT model expression and compared with similar values of complexation of the metal ions Am³⁺, Eu³⁺, UO₂ ²⁺, PuO₂ ²⁺, Np⁴⁺, Ni²⁺ and Co²⁺. The speciation of NpO₂ ⁺-o-silicate/carbonate system has been calculated as a function of pcH under ground water conditions. On leave from Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai-400 085, India.     

Opposite effect of Li<Superscript>+</Superscript> codoping on the upconversion emissions of Er<Superscript>3+</Superscript>-doped TiO<Subscript>2</Subscript> powders

The Er³⁺-Li⁺ codoped TiO₂ powders have been prepared by the non-aqueous sol–gel method. The green and red upconversion emissions centered at about 526, 550 and 663 nm were observed by the ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of Er³⁺, respectively. Li⁺ codoping has opposite effect on the upconversion emissions intensities for Er³⁺-doped TiO₂ at sintering temperatures of 1,073 and 1,273 K. At 1,073 K, the Er³⁺-doped TiO₂ phase transition from anatase to rutile was accelerated with increasing Li⁺ codoping concentration, leading to the increase of crystal field symmetry of Er³⁺, thus the upconversion emissions intensities decreased. At 1,273 K, Li⁺ codoping had no effect on the phase structure of Er³⁺-doped TiO₂ and only increased the Er–O bond length, it indicated that the upconversion emissions intensities greatly enhanced because of the decrease of crystal field symmetry of Er³⁺.     

Influence of composition on corroding process of Na<Subscript>2</Subscript>O-K<Subscript>2</Subscript>O-CaO-ZrO<Subscript>2</Subscript>-SiO<Subscript>2</Subscript> glasses

The corroding process of six glasses of the Na₂O-K₂O-CaO-ZrO₂-SiO₂ system with ZrO₂content 0–2.13 mass % by water was observed during static tests at 121°C and pressure of 0.25 MPa in steam sterilizer. Significant increase of Na⁺ and K⁺ content in leachates was observed after the addition of ZrO₂ into glass. Further increase of the content of ZrO₂ in glasses slowed down the rate of Na⁺ and K⁺ leaching. The leaching process of SiO₂ as well as Na⁺, K⁺, and Ca²⁺ ions was evaluated on the basis of comparison with model leaching processes. Variation of the concentrations of Na⁺, K⁺, Ca²⁺, and SiO₂ in leachates with time was described by empirical equation. Observed changes in the initial leaching rates of Na⁺, K⁺, Ca²⁺, and SiO₂ can be ascribed to the content of ZrO₂ in glasses. The presence of ZrO₂ in glasses reduced the overall rate of glass dissolution.     

Photocatalysis enhancement of CaAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2+</Superscript>, Nd<Superscript>3+</Superscript>@TiO<Subscript>2</Subscript> composite powders

CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders were synthesized by a sol–gel method under mild conditions (i.e. low temperature and ambient pressure). The as-prepared powders were characterized by transmission electron microscopy (TEM) and analyzed by X-ray diffraction (XRD). The photocatalytic behavior of the TiO₂-base surfaces was evaluated by the degradation of nitrogen monoxide gas. It suggested that CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders were composed of anatase titania and that CaAl₂O₄:Eu²⁺, Nd³⁺. TiO₂ particles were deposited on the surface of CaAl₂O₄:Eu²⁺, Nd³⁺ to form uniform film. CaAl₂O₄:Eu²⁺, Nd³⁺@TiO₂ composite powders exhibited higher photocatalytic activity compared with pure TiO₂ under visible light. And the result also clearly indicated that the long afterglow phosphor absorbed and stored lights for the TiO₂ to remain photocatalytic activity in the dark.     

Photochemical substitution of benzene in the iron cyclohexadienyl complex [(η<Superscript>5</Superscript>-C<Subscript>6</Subscript>H<Subscript>7</Subscript>)Fe(η-C<Subscript>6</Subscript>H<Subscript>6</Subscript>)]<Superscript>+</Superscript>

The visible light irradiation of the [(η⁵-C₆H₇)Fe(η-C₆H₆)]⁺ cation (1) in acetonitrile resulted in the substitution of the benzene ligand to form the labile acetonitrile species [(η⁵-C₆H₇)Fe(MeCN)₃]⁺ (2). The reaction of 1 with Bu^tNC in MeCN produced the stable isonitrile complex [(η⁵-C₆H₇)Fe(Bu^tNC)₃]⁺ (3). The photochemical reaction of cation 1 with pentaphosphaferrocene Cp*Fe(η-cyclo-P₅) afforded the triple-decker cation with the bridging pentaphospholyl ligand, [(η⁵-C₆H₇)Fe(μ-η:η-cyclo-P₅)FeCp*]⁺ (4). The latter complex was also synthesized by the reaction of cation 2 with Cp*Fe(η-cyclo-P₅). The structure of the complex [3]PF₆ was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2088–2091, November, 2007.     

Effect of the Support on the Nature of Metal-Promoter Interactions in Ru-Cs<Superscript>+</Superscript>/MgO and Ru-Cs<Superscript>+</Superscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts for Ammonia Synthesis

The Ru-Cs⁺/MgO and Ru-Cs⁺/γ-Al₂O₃ catalysts, which were prepared by an impregnation method using RuOHCl₃ and Cs₂CO₃ as precursor compounds and reduced with H₂ at 450°C, are characterized by X-ray diffraction, high-resolution transmission electron microscopy (with X-ray microanalysis), and X-ray photoelectron spectroscopy (XPS). The Cs⁺/MgO(Al₂O₃) systems, Ru-Cs⁺ black, and model systems prepared by cesium sputtering onto polycrystalline ruthenium foil are studied as reference samples. It is found that, in the Ru-Cs⁺/MgO sample, cesium is present as a Cs_{2 + x}O cesium suboxide, which weakly interacts with the support, localized on the surface of Ru particles or near them. In the case of Ru-Cs⁺/γ-Al₂O₃, cesium occurs as a species that is tightly bound to the support; this is likely surface cesium aluminate, which prevents promoter migration to Ru particles. The Ru-Cs⁺/MgO sample exhibits a considerable shift of the Ru3d line in the XPS spectra toward lower binding energies, as compared to the bulk metal. It is hypothesized that this shift is due to a decrease in the electron work function from the surface of ruthenium because of the polarizing effect of Cs⁺ ions in contact with Ru particles. Based on the experimental results, the great difference between the catalytic activities of the Ru-Cs⁺/MgO and Ru-Cs⁺/γ-Al₂O₃ systems in ammonia synthesis at 250–400°C and atmospheric pressure is explained.     

Novel large heteropolymetalate complexes formed from Ni(II) and cryptate [As<Subscript>4</Subscript>W<Subscript>40</Subscript>O<Subscript>140</Subscript><Superscript>28-</Superscript>

The heteropolytungstate (NH4)₂₀[Na2(H₂O)₂Ni(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀] · 61H₂O is obtained by the reaction of Na₂₇[NaAs₄W₄₀O₁₄₀] · 60H₂O with NiCl₂ · 6H₂O and NH₄Cl in pH≈4.0. The structure and chemical composition are determined by X-ray diffraction analysis and element analysis. The crystal data and main structure refinement are: a = 1.33135(18) nm, b = 1.9722(3) nm, c = 3.6430(5) nm, α = 78.010(2)°, β = 82.145(2)δ, γ = 74.385(2)°, V = 8.978(2) nm³, triclinic crystal system, space group: P1, Z = 2, R1 = 0.0512, and wR2 = 0.0684(I >2σ). The four S2 sites of the big cyclic ligand [As₄W₄₀O₁₄₀]^28- are occupied by two Na⁺ and two Ni²⁺ respectively, and each site supplies four O_d coordinating to metal ion. The coordination number of Ni²⁺ is six, and that of two Na⁺ is five and six respectively. The third Ni²⁺ locates outside the cyclic [As₄W₄₀O₁₄₀]^28- and connects with one O_d, and its coordination number is six.     

Cation binding by 2<Superscript>1</Superscript>,3<Superscript>1</Superscript>-diphenyl-l <Superscript>2</Superscript>,4<Superscript>2</Superscript>-dioxo-7,10,13-trioxa-1,4(3,1)-diquinoxalina-2 (2,3),3(3,2)-diindolizinacyclopentadecaphane and its acyclic analog

The binding of cations Li⁺, Na⁺, K⁺, Cs⁺, Ag⁺, Zn²⁺, Ni²⁺, Co²⁺, NH₄ ⁺ (group I), H⁺, Mg²⁺, Al³⁺, Ga³⁺ (group II), and Ca²⁺, Pb²⁺ (group III) by 2¹,3¹-diphenyl-l ²,4²-dioxo- 7,10,13-trioxa-l,4(3,1)-diquinoxalina-2(2,3),3(3,2)-diindolizinacyclopentadecaphane (1), which contains two indolizine and two quinoxaline fragments and 3,6,9-trioxaundecanes spacer, and by its acyclic analog (2) was studied using cyclic voltammetry in MeCN/0.1 M Bu₄NBF₄. It was concluded that the ions of group I are not bound by these compounds, the ions of group II exhibit the reversible redox-switched binding by the carbamoyl groups of the quinoxaline fragments, whereas the ions of group III are bound not only by the initial compounds and radical cations 1 and 2, but also by dication 1. This binding of the Ca²⁺ and Pb²⁺ ions stabilizes dication 1.     

Hexametavanadates M<Stack><Subscript>4</Subscript><Superscript>+</Superscript></Stack>M<Superscript>2+</Superscript>(VO<Subscript>3</Subscript>)<Subscript>6</Subscript>: Thermal stability and luminescent characteristics

Rhombohedral hexametavanadates K₄Sr(VO₃)₆, K₄Ba(VO₃)₆, Rb₄ Ba(VO₃)₆, and Cs₄Ba(VO₃)₆ melt incongruently in the temperature range of 491 to 600°C. Cooling of peritectic melts yields mixtures of compounds typical of M₂⁺O-M²⁺O-V₂O₅ systems, far from equilibrium and depending on the cooling kinetics. The vanadate Cs₄Ba(VO₃)₆ undergoes reversible polymorphic transformation at 360°C. All compounds show broad-band luminescence with a maximum of the luminescence spectrum at 490–590 nm with three types of excitation. The vanadates K₄Sr(VO₃)₆ and Rb₄Ba(VO₃)₆ show the highest luminescence intensity at room temperature. The latter is also most efficient at liquid nitrogen temperatures. The luminescence spectra depend on the excitation of vanadates. Three hypotheses were put forward to interpret this finding. The nature of luminescence is attributed to the relaxation of electronic excitation in [VO₄]³⁻ structural tetrahedra present in the vanadates. The performance characteristics of luminophores were determined. These luminophores may be promising as X-ray luminescent screens, radioluminescence indicators, and light-emitting diode devices.     

Theoretical study of the mechanism for C-H bond activation in spin-forbidden reaction between Ti<Superscript>+</Superscript> and C<Subscript>2</Subscript>H<Subscript>4</Subscript>

The mechanism of the spin-forbidden reaction Ti⁺(⁴F, 3d²4s¹) + C₂H₄→TiC₂H₂ ⁺ (²A₂) + H₂ on both doublet and quartet potential energy surfaces has been investigated at the B3LYP level of theory. Crossing points between the potential energy surfaces and the possible spin inversion process are discussed by means of spin-orbit coupling (SOC) calculations. The strength of the SOC between the low-lying quartet state and the doublet state is 59.3 cm⁻¹ in the intermediate complex IM1-⁴B₂. Thus, the changes of its spin multiplicity may occur from the quartet to the doublet surface to form IM1-²A₁, leading to a sig-nificant decrease in the barrier height on the quartet PES. After the insertion intermediate IM2, two distinct reaction paths on the doublet PES have been found, i.e., a stepwise path and a concerted path. The latter is found to be the lowest energy path on the doublet PES to exothermic TiC₂H₂ ⁺(²A₂) + H₂ products, with the active barrier of 4.52 kcal/mol. In other words, this reaction proceeds in the following way: Ti⁺+C₂H₄→⁴IC→IM1-⁴B₂→^4,2ISC→IM1-²A₁→[²TS_ins]→IM2→[²TS_MCTS]→IM5→TiC₂H₂ ⁺(²A₂)+H₂. Supported by ‘Qinglan’ Talent Engineering Funds by Tianshui Normal University.     

Composition and structure of solid solutions in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>-V<Stack><Subscript>2</Subscript><Superscript>5+</Superscript></Stack>O<Subscript>5</Subscript> system with the structure sillenite

In the Bi₂O₃-SiO₂-V₂⁵⁺+O₅ system, single crystal solid solutions of the sillenite family of the general composition Bi₂₄(Bi,Si,V)₂O₄₀ are obtained by a hydrothermal method and for the first time characterized by neutron and X-ray diffraction analysis. The tetrahedral position is found to contain vanadium ions with different formal charges (V⁴⁺ and V⁵⁺) responsible for green and orange colors, respectively, of the samples. For the first time, for some sillenites of this system dissymmetrization of the structure (a transition from the I23 space group into P23) is revealed, which is caused by the presence of several atoms in one crystallographic position and also by crystal growth conditions.     

Optical energy storage properties of Sr<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>2+</Superscript>,R<Superscript>3+</Superscript> persistent luminescence materials

The details of the mechanism of persistent luminescence were probed by investigating the trap level structure of Sr₂MgSi₂O₇:Eu²⁺,R³⁺ materials (R: Y, La-Lu, excluding Pm and Eu) with thermoluminescence (TL) measurements and Density Functional Theory (DFT) calculations. The TL results indicated that the shallowest traps for each Sr₂MgSi₂O₇:Eu²⁺,R³⁺ material above room temperature were always ca. 0.7 eV corresponding to a strong TL maximum at ca. 90 °C. This main trap energy was only slightly modified by the different co-dopants, which, in contrast, had a significant effect on the depths of the deeper traps. The combined results of the trap level energies obtained from the experimental data and DFT calculations suggest that the main trap responsible for the persistent luminescence of the Sr₂MgSi₂O₇:Eu²⁺,R³⁺ materials is created by charge compensation lattice defects, identified tentatively as oxygen vacancies, induced by the R³⁺ co-dopants.     

Near-infrared quantum cutting in Tb<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript>-doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript> nanophosphors

Properties of the quantum-cutting phosphors are dependent on various factors such as dopant concentration, crystallinity, homogeneity, particle size and surface morphology. Effective control of the above parameters can enhance the quantum-cutting ability of the phosphor material. Nano-sized particles of Y₂O₃:Tb³⁺,Yb³⁺ were prepared with a solution-based co-precipitation method and subsequent calcination. Effective control of the reaction parameters and doping concentration helped to produce uniform nanostructures with high quantum-cutting efficiency up to 181.1 %. The energy transfer mechanism between Tb³⁺ and Yb³⁺ was studied by considering their spectroscopic properties and time-resolved spectroscopy. The high efficiency and small particle size of the quantum-cutting phosphor Y₂O₃:Tb³⁺,Yb³⁺ make it a suitable candidate for its application in solar cells.     

Layered LiNi<Subscript>0.80</Subscript>Co<Subscript>0.15</Subscript>Al<Subscript>0.05</Subscript>O<Subscript>2</Subscript> as cathode material for hybrid Li<Superscript>+</Superscript>/Na<Superscript>+</Superscript> batteries

LiNi_0.80Co_0.15Al_0.05O₂ (NCA) is explored to be applied in a hybrid Li⁺/Na⁺ battery for the first time. The cell is constructed with NCA as the positive electrode, sodium metal as the negative electrode, and 1 M NaClO₄ solution as the electrolyte. It is found that during electrochemical cycling both Na⁺ and Li⁺ ions are reversibly intercalated into/de-intercalated from NCA crystal lattice. The detailed electrochemical process is systematically investigated by inductively coupled plasma-optical emission spectrometry, ex situ X-ray diffraction, scanning electron microscopy, cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy. The NCA cathode can deliver initially a high capacity up to 174 mAh g^?1 and 95% coulombic efficiency under 0.1 C (1 C?=?120 mA g^?1) current rate between 1.5–4.1 V. It also shows excellent rate capability that reaches 92 mAh g^?1 at 10 C. Furthermore, this hybrid battery displays superior long-term cycle life with a capacity retention of 81% after 300 cycles in the voltage range from 2.0 to 4.0 V, offering a promising application in energy storage.     

Solubility and hydrolysis of lutetium at different [Lu<Superscript>3+</Superscript>]<Subscript>initial</Subscript>

Solubility product (Lu(OH)_3(s)⇆Lu³⁺+3OH⁻) and first hydrolysis (Lu³⁺+H₂O⇆Lu(OH)²⁺+H⁺) constants were determined for an initial lutetium concentration range from 3.72·10⁻⁵ mol·dm⁻³ to 2.09·10⁻³ mol·dm⁻³. Measurements were made in 2 mol·dm⁻³ NaClO₄ ionic strength, under CO₂-free conditions and temperature was controlled at 303 K. Solubility diagrams (pLu_aq vs. pC _H) were determined by means of a radiochemical method using ¹⁷⁷Lu. The pC _H for the beginning of precipitation and solubility product constant were determined from these diagrams and both the first hydrolysis and solubility product constants were calculated by fitting the diagrams to the solubility equation. The pC _H values of precipitation increases inversely to [Lu³⁺]_initial and the values for the first hydrolysis and solubility product constants were log₁₀ β* _Lu,H = −7.92±0.07 and log₁₀ K*_sp,Lu(OH)3 = −23.37±0.14. Individual solubility values for pC _H range between the beginning of precipitation and 8.5 were S _Lu3+ = 3.5·10⁻⁷ mol·dm⁻³, S _Lu(OH)2+ = 6.2·10⁻⁷ mol·dm⁻³, and then total solubility was 9.7·10⁻⁷ mol·dm⁻³.     

DFT studies on the structures and stabilities of N<Subscript>5</Subscript><Superscript>+</Superscript>-containing salts

Density functional theory (DFT) methods have been applied to study the properties of series of N₅ ⁺ salts. The thermal stabilities of the crystals are evaluated based on the reaction enthalpy (ΔH) and free energy change (∆G) of the salts when they dissociate into neutral products. The energy outputs of salts in explosion indicate that all N₅ ⁺ salts yield large energy except for N₅SbF₆ and N₅Sb₂F₁₁. Considering the released energy and thermal stability, (N₅)₂SnF₆, N₅PF₆, N₅BF₄, and N₅SO₃F may be potential candidates of very energetic explosives.     

Molecular modeling of hydration properties of hydrophobic ions Li<Superscript>+</Superscript>@C<Subscript>60</Subscript> and K<Superscript>+</Superscript>@C<Subscript>60</Subscript>

The Gibbs free energies of solvation (ΔG _s) and the electronic structures of endohedral metallofullerenes M⁺@C₆₀ (M⁺= Li⁺, K⁺) were calculated within the framework of the density functional theory and the polarizable continuum model. In water environment, the equilibrium position of K⁺ is at the center of the fullerene cavity whereas that of Li⁺ is shifted by 0.14 nm toward the fullerene cage. The Li⁺ cation is stabilized by interactions with both the fullerene and solvent. The equilibrium structures of both endohedral metallofullerenes are characterized by very close ΔG _s values. In particular, the calculated ΔG _s values for K⁺@C₆₀ are in the range from −124 to −149 kJ mol⁻¹ depending on the basis set and on the type of the density functional. Molecular dynamics simulations (TIP3P H₂O, OPLS force field, water sphere of radius 1.9 nm) showed that the radial distribution functions of water density around C₆₀ and M⁺@C₆₀ are very similar, whereas orientations of water dipoles around the endohedral metallofullerenes resemble the hydration pattern of isolated metal ions.     

Radiation-chemical yield of excited neodymium(III) in laser liquids POCl<Subscript>3</Subscript>-MCl<Subscript>n</Subscript>-<Superscript>235</Superscript>UO<Subscript>2</Subscript><Superscript>2+</Superscript>-Nd<Superscript>3+</Superscript> (M = Ti,Zr, Sn,or Sb)

Results of measurements of the yield of Nd³⁺ radioluminescence photons in inorganic laser liquids POCl₃-MCl_n-²³⁵UO ₂ ²⁺ -Nd³⁺ (M = Ti, Zr, Sn, or Sb) during homogeneous excitation by uranium α-particles are presented. It was found that the intensity of radioluminescence corresponding to the ⁴ F _3/2 → ⁴ I _11/2 transition in neodymium ions depends on the solvent composition. Data on the radiation-chemical yield, G, of excited neodymium ions in the POCl₃-MCl_n-²³⁵UO ₂ ²⁺ -Nd³⁺ (M = Ti, Zr, Sn, or Sb) system were obtained. At a neodymium concentration of 0.25 mol/l, the values of G for the excited ions were 0.60 ± 0.10, 0.84 ± 0.10, 1.20 ± 0.10, and 1.64 ± 0.16 ion/100 eV in solutions with TiCl₄, ZrCl₄, SnCl₄, and SbCl₅, respectively. The maximum yields of excited ions estimated at G = 1.68 ± 0.10 and 2.20 ± 0.24 ion/100 eV were obtained for the solutions with SnCl₄ and SbCl₅, respectively, at neodymium ion concentrations above 0.4 mol/l.     

Gas phase structure of micro-hydrated [Mn(ClO<Subscript>4</Subscript>)]<Superscript>+</Superscript> and [Mn<Subscript>2</Subscript>(ClO<Subscript>4</Subscript>)<Subscript>3</Subscript>]<Superscript>+</Superscript> ions probed by infrared spectroscopy

Gas-phase infrared photodissociation spectroscopy is reported for the microsolvated [Mn(ClO₄)(H₂O) _n ]⁺ and [Mn₂(ClO₄)₃(H₂O) _n ]⁺ complexes from n = 2 to 5. Electrosprayed ions are isolated in an ion-trap where they are photodissociated. The 2600–3800 cm⁻¹ spectral region associated with the OH stretching mode is scanned with a relatively low-power infrared table-top laser, which is used in combination with a CO₂ laser to enhance the photofragmentation yield of these strongly bound ions. Hydrogen bonding is evidenced by a relatively broad band red-shifted from the free OH region. Band assignment based on quantum chemical calculations suggest that there is formation of water—perchlorate hydrogen bond within the first coordination shell of high-spin Mn(II). Although the observed spectral features are also compatible with the formation of structures with double-acceptor water in the second shell, these structures are found relatively high in energy compared with structures with all water directly bound to manganese. Using the highly intense IR beam of the free electron laser CLIO in the 800–1700 cm⁻¹, we were also able to characterize the coordination mode (η²) of perchlorate for two clusters. The comparison of experimental and calculated spectra suggests that the perchlorate Cl—O stretches are unexpectedly underestimated at the B3LYP level, while they are correctly described at the MP2 level allowing for spectral assignment.     

Functionalization of one or two methyl groups in the [Cp*<Subscript>2</Subscript>RuBr]<Superscript>+</Superscript>Br<Superscript>−</Superscript> complex in the reaction with bromine

The reaction of [Cp*₂RuBr]⁺Br⁻ with bromine in CH₂Cl₂ (CD₂Cl₂) in an inert atmosphere at room temperature produces the complexes [Cp*Ru(Br)C₅Me₄CH₂Br]⁺Br₃ ⁻ (syn conformer), [Cp*Ru(Br)C₅Me₃(CH₂Br)₂]⁺ (syn and anti conformers), and [Ru(Br)(C₅Me₄CH₂Br)₂]⁺ (syn conformer). All complexes were characterized by ¹H and ¹³C NMR spectroscopy; the former complex, by elemental analysis. These complexes were also prepared by the reaction of [Cp*RuC₅Me₄CH₂]⁺BF₄ ⁻ with bromine in CH₂Cl₂. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2712–2718, December, 2005.