Measurement of the rate constants of the reactions of the chlorine atom with C<Subscript>3</Subscript>F<Subscript>7</Subscript>I and CF<Subscript>3</Subscript>I using the resonance fluorescence of chlorine atoms

The rate constants of the reactions of the chlorine atom with C₃F₇I (k ₁) and CF₃I (k ₂) have been measured using the resonance fluorescence of chlorine atoms in a flow reactor at 295 K: k ₁ = (5.2 ± 0.3) × 10⁻¹² cm³ molecule⁻¹ s⁻¹ and k ₂ = (7.4 ± 0.6) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹. No iodine atoms have been detected in the reaction products.     

Effect of structural features of molecules (Cl<Subscript>3</Subscript>PNZ)<Subscript>2</Subscript> (Z = CH<Subscript>3</Subscript> and CH<Subscript>2</Subscript>CH<Subscript>2</Subscript>Cl) on the position exchange of chlorine atoms in the P-Cl fragments

Based on the analysis of structural parameters of molecules (Cl₃PNCH₃)₂ (I) and (Cl₃PNCH₂CH₂Cl)₂ (II) by the quantum-chemical nonempirical calculations the following was revealed. The structure of I and II dimers has geometric features, which have a decisive influence on the degree of inhibition of positional exchange of the chlorine atoms in the P-Cl fragments known for the chlorine derivatives of pentacoordinated phosphorus atom. The obstacles to this dynamic process in the mentioned intramolecular dimers is shown to result from the spatial nonvalent interactions due to the short contacts of the chlorine and hydrogen atoms.     

Radical–molecule reaction CH<Subscript>2</Subscript>Cl + NO<Subscript>2</Subscript>: a mechanistic study

The radical–molecule reaction mechanism of CH₂Cl with NO₂ has been explored theoretically at the B3LYP/6–311G(d,p) and MC–QCISD (single-point) levels of theory. Our results indicate that the title reaction proceeds mostly through singlet pathways, less go through triplet pathways. The initial association between CH₂Cl and NO₂ is found to be the carbon-to-nitrogen attack forming the adduct a H₂ClCNO₂ with no barrier, followed by isomerization to b ₁ H₂ClCONO-trans which can easily convert to b ₂ H₂ClCONO-cis. Subsequently, the most feasible pathway is the C–Cl and O–N bonds cleavage along with the N–Cl bond formation of b (b ₁ , b ₂ ) leading to product P ₁ CH₂O + ClNO, which can further dissociate to give P ₅ CH₂O + Cl + NO. The second competitive pathway is the 1,3-H-shift associated with O–N bond rupture of b ₁ to form P ₂ CHClO + HNO. Because the intermediates and transition states involved in the above two favorable channels all lie below the reactants, the CH₂Cl+NO₂ reaction is expected to be rapid, as is confirmed by experiment. The present results can lead us to understand deeply the mechanism of the title reaction and may be helpful for further experimental investigation of the reaction.     

Homogeneous catalytic fluoroalkylation of thiophenols,phenols and pyrrole by Freons BrCF<Subscript>2</Subscript>CF<Subscript>2</Subscript>Br and CF<Subscript>2</Subscript>ClCFCl<Subscript>2</Subscript>

The use of sulfur dioxide as an electron transfer mediator in the presence of nitrogen bases permits the rather selective fluoroalkylation of thiophenols, phenols, and pyrrole by Freons BrCF₂CF₂Br and CF₂ClCFCl₂ under mild conditions. In the case of thiophenols, the fluoroalkylation occurs to give polyfluoroalkyl aryl sulfides, while phenols and pyrrole are alkylated in the ring. Effects were found for the electronic structure of the substrates and basicity of the medium (pK_α of the pyridines) on the oxidation-reduction properties of the reagents and the efficiency of the reactions studied. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 5, pp. 315–322, September–October, 2007.     

Thermodynamic Properties of AgIn<Subscript>2</Subscript>Te<Subscript>3</Subscript>I and AgIn<Subscript>2</Subscript>Te<Subscript>3</Subscript>Br,Determined by EMF Method

Differential thermal analysis (DTA), X-ray diffraction (XRD), and electromotive force (EMF) are used to triangulate Ag–In–Te–I(Br) systems in the vicinity of compounds AgIn₂Te₃I and AgIn₂Te₃Br. The three-dimensional position of the AgIn₂Te₃I–InTe–Ag₂Te–AgI and AgIn₂Te₃Br–InTe–Ag₃TeBr phase areas with respect to the figurative points of silver is used to create equations of potential-determining chemical reactions. The potential-determining reactions are conducted in (?)C|Ag|Ag₃GeS₃I(Br) glass|D|C(+) electrochemical cells (ECCs), where C stands for inert (graphite) electrodes, Ag and D are ECC electrodes (D denotes alloys of one-, three-, and four-phase areas), and Ag₃GeS₃I and Ag₃GeS₃Br glasses are membranes with purely ionic Ag⁺ conductivity. Linear parts of the temperature dependences of the cell EMFs are used to calculate the standard integral thermodynamic functions of saturated solid solutions based on AgIn₂Te₃I and AgIn₂Te₃Br, and the relative partial thermodynamic functions of silver in the stoichiometric quaternary compounds.     

Investigation into the formation of heteronuclear clusters of formula [{Ru<Subscript>6</Subscript>C(CO)<Subscript>16</Subscript>Ag<Subscript>2</Subscript>X}<Subscript>2</Subscript>]<Superscript>2−</Superscript> (X = Cl,Br or I)

Reaction of [Ru₆C(CO)₁₆]²⁻ with an excess of AgX (X = Cl, Br or I) affords heteronuclear clusters of formula [{Ru₆C(CO)₁₆Ag₂X}₂]²⁻ in 80% yield, which for X = I and X = Br/Cl were crystallographically characterised. The formation of the cluster was followed in solution using electrospray ionisation mass spectrometry (ESI-MS), which revealed the presence of a wide range of clusters with the general formula [{Ru₆C(CO)₁₆} _x Ag _y X _z ]^{(2x−y+z)−} where x = 1 or 2, y = 1, 2, 3 or 4 and z = 0, 1 or 2. The high yield of the product despite the evident complicated solution speciation is attributed to selective crystallisation of the observed compound driving the equilibrium toward this product.     

Reactions of Cr atoms with NO,N<Subscript>2</Subscript>O,CO<Subscript>2</Subscript>, NO<Subscript>2</Subscript>, and SO<Subscript>2</Subscript> molecules

Experimental results on the interaction of Cr atoms with various oxygen-containing molecules (NO, N₂O, CO₂, NO₂, and SO₂) at high temperatures (>1000 K) are presented. It is demonstrated that activation barrier for spin-forbidden reactions is higher, all other things being equal. For the reaction of Cr atoms with N₂O, an interpolated temperature dependence of the rate constant, based on the high-temperature measurements conducted in the present work and the published low-temperature data, is proposed.     

Measurement of the reaction rate constants of oxygen atoms with chlorine and iodomethane using a resonance fluorescence technique

The following reaction rate constants of oxygen atoms with iodomethane and chlorine were measured using resonance fluorescence under jet conditions at 298 K: k ₁ = (2.4 ± 0.5) × 10–15 and k ₂ = (6.9 ± 0.2) × 10⁻¹⁴ cm³/s, respectively.     

The reaction between [RuCl<Subscript>2</Subscript>(PPh<Subscript>3</Subscript>)<Subscript>3</Subscript>] and hydroxyquinoline carboxylic acid

The reactions of [RuCl₂(PPh₃)₃] with 8-hydroxy-2-methyl-quinoline-7-carboxylic acid was examined, and a novel ruthenium(II) complex—[Ru(PPh₃)₂(C₅H₈NO)₂]—was obtained. The compound was studied by IR, UV–vis spectroscopy, and X-ray crystallography. The molecular orbital diagram of the complex was calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compound were calculated using the time-dependent DFT method, and the UV–vis spectrum of the compound was discussed, on this basis. The luminescence property of the [Ru(PPh₃)₂(C₅H₈NO)₂]was examined.     

Hot atom chemical behavior of tritium in neutron-irradiated Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript> and Li<Subscript>2</Subscript>ZrO<Subscript>3</Subscript>

The annihilation behavior of irradiation defects induced in neutron-irradiated Li₂TiO₃ and Li₂ZrO₃ were investigated with the tritium release behavior. It was revealed that the common characteristics in both samples were that the annihilation process of irradiation defects consisted of two first-order processes and E’-center could act as tritium trapping site, and otherwise was the way how the E’-center annihilated. The difference was suggested to attribute to the mobility of M as M⁴⁺ (or M³⁺, etc.).     

Structural investigation of [Au(en)<Subscript>2</Subscript>]Cl(ReO<Subscript>4</Subscript>)<Subscript>2</Subscript> and [Au(en)<Subscript>2</Subscript>](ReO<Subscript>4</Subscript>)<Subscript>3</Subscript> complexes

Novel complex salts [Au(en)₂]Cl(ReO₄)₂ (I) and [Au(en)₂](ReO₄)₃ (II), en = ethylenediamine, are obtained. Their crystal structures are determined by single crystal X-ray diffraction. Complex I crystallizes in the triclinic crystal system: a = 6.2172(7) Å, b = 7.1644(8) Å, c = 8.8829(8) Å, α = 96.605(4)°, β = 110.000(4)°, γ = 97.802(4)°, P-1 space group, Z = 1, d _x = 3.905 g/cm³; complex II crystallizes in the monoclinic crystal system: a = 15.244(2) Å, b = 7.6809(8) Å, c = 9.3476(12) Å, β = 127.004(3)°, C2 space group, Z = 4, d _x = 4.057 g/cm³.     

Preparation and Crystal Structure of MnBiS<Subscript>2</Subscript>Br

Summary. Black single crystals of MnBiS₂Br were obtained by the reaction of stoichiometric amounts of α-MnS, Bi, S, and BiBr₃ (3:2:3:1) at 600°C for 4 weeks. The compound crystallises in the monoclinic system, space group C2/m, with a = 12.767(2), b = 3.9468(4), c = 9.574(1) ?, β = 90.87(2)°, and Z = 4. The crystal structure refinement based on 720 reflections converged at R = 0.0244 and wR2 = 0.0579, respectively. MnBiS₂Br forms a layer structure consisting of MnS₆ octahedra, MnS₂Br₄ octahedra, and BiS₃₊₂ pyramids.     

Measuring the rate constant of the reaction between carbon monoxide and iodine oxide at 298–363 K by the resonance fluorescence method

The rate constant of the reaction between the IO radical and carbon monoxide has been measured by the iodine atom resonance fluorescence method in the temperature range from 298 to 363 K. The reaction mainly takes place on the wall of the reactor.     

The Synthesis and Characterization of Ru<Subscript>2</Subscript>(DMBA-X)<Subscript>4</Subscript>Cl<Subscript>2</Subscript> with X as Br and I

New N,N′-dimethylbenzamidine ligands bearing para-Br (HDMBA-Br) and para-I (HDMBA-I) substituents were prepared and crystallographically characterized. The ligand exchange reaction between Ru₂(OAc)₄Cl and HDMBA-X (X = Br and I) afforded the new Ru₂(III) compounds, namely Ru₂(DMBA-X)₄Cl₂, in excellent yields. These new compounds were also characterized with cyclic voltammetric and single crystal X-ray diffraction techniques. Dedicated to the memory of Professor F. A. Cotton.     

Thermal decomposition studies of [Ni(NH<Subscript>3</Subscript>)<Subscript>6</Subscript>]X<Subscript>2</Subscript> (X = Cl,Br) in the solid state using TG-MS and TR-XRD

Detailed investigation on the thermal behaviour of hexaamminenickel(II) chloride and hexaamminenickel(II) bromide has been carried out by means of simultaneous TG/DTA coupled online with mass spectroscopy (TG-MS) and temperature-resolved X-ray diffraction (TR-XRD). Evolved gas analyses by TG-MS revealed the presence of NH₂, NH, N₂ and H₂ fragments in addition to ammonia during the deamination process. These transient species resulted due to the fragmentation of the evolved ammonia during pyrolysis. The intermediates formed during the thermal deamination stages were monitored by in situ TR-XRD. The final product of the decomposition was found to be nano size metallic nickel in both cases. Morphology of the complexes, intermediates and the residue formed at various decomposition stages was analysed by scanning electron microscope (SEM). Kinetic analyses using isoconversional method for deamination and dehalogenation reaction show that the activation energies vary with the extent of conversion, indicating the multi-step nature of these solid state decomposition reactions.     

Reaction of Methyl Diazoacetate with Amines Catalyzed by Ru<Subscript>2</Subscript>(OAc)<Subscript>4</Subscript>Cl

Reactions of primary and secondary amines with methyl diazoacetate in the presence of Ru₂(OAc)₄Cl gave the corresponding N-substituted glycine methyl esters in almost quantitative yield. Catalytic decomposition of methyl diazoacetate generates methoxycarbonylcarbene which is inserted into the N-H bond of amines with high regioselectivity.     

Synthesis of cyclopropane-containing organoaluminum compounds by the reaction of acetylenes with CH<Subscript>2</Subscript>I<Subscript>2</Subscript> and Et<Subscript>3</Subscript>Al

Reactions of disubstituted and terminal acetylenes with CH₂I₂ and Et₃Al in the molar ratio 1: 4: 6 lead to the selective formation of organoaluminum compounds containing di-, tri-, or tetrasubstituted cyclopropane fragments depending on the nature of acetylene and reaction conditions.     

Crystal structure of Tl<Subscript>5</Subscript>{[Nb<Subscript>2</Subscript>S<Subscript>4</Subscript>Br<Subscript>8</Subscript>]Br}

By the high-temperature reaction of Nb₂S₄Br₄ and TlBr a thallium salt of the anionic cluster complex [Nb₂S₄Br₈]^4? is obtained. Its crystal structure is determined by X-ray structural analysis. The complex is also characterized by Raman spectroscopy and electrospray-mass-spectrometry.     

Dielectric constant and dielectric relaxation in aqueous solutions of K<Subscript>2</Subscript>[PdCl<Subscript>4</Subscript>] and K<Subscript>2</Subscript>[PtCl<Subscript>4</Subscript>]

The MW-dielectric properties of aqueous solutions of K₂[PtCl₄] (I) and K₂[PdCl₄] (II) were studied at 298 and 313 K in the frequency range (12–25 GHz) corresponding to the maximum dielectric constant dispersion for water and aqueous solutions of these salts. The low-frequency conductivities were measured. The static dielectric constant, the dielectric relaxation time, and the enthalpy of activation of the dielectric relaxation of the solutions were determined. Compared to pure water, in solutions of salts I and II, the orientational mobility of water molecules is increased and the network of H-bonds is violated more strongly than that of most other ions with hydrophilic hydration. It was demonstrated for the first time that dielectric spectroscopy can be used for analyzing complexation processes in systems containing aqua and hydroxo chloride complexes of metals.     

Synthesis and characterization of the [Ru<Subscript>3</Subscript>O(CH<Subscript>3</Subscript>COO)<Subscript>6</Subscript>(py)<Subscript>2</Subscript>(BPE)Ru(bpy)<Subscript>2</Subscript>Cl](PF<Subscript>6</Subscript>)<Subscript>2</Subscript> dimer

The polymetallic [Ru₃O(CH₃COO)₆(py)₂(BPE)Ru(bpy)₂Cl](PF₆)₂ complex (bpy = 2,2′-bipyridine, BPE = trans-1,2-bis(4-pyridil)ethylene and py = pyridine) was assembled by the combination of an electroactive [Ru₃O] moiety with a [Ru(bpy)₂(BPE)Cl] photoactive centre, and its structure was determined using positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS) spectrometry. The [Ru₃O(CH₃COO)₆(py)₂(BPE)Ru(bpy)₂Cl]²⁺ doubly charged ion of m/z 732 was mass-selected and subject to 15 eV collision-induced dissociation, leading to a specific dissociation pattern, diagnostic of the complex structure. The electronic spectra display broad bands at 409, 491 and 692 nm ascribed to the [Ru(bpy)₂(BPE)] charge-transfer bands and to the [Ru₃O] internal cluster transitions. The cyclic voltammetry shows five reversible waves at −1.07 V, 0.13 V, 1.17 V, 2.91 V and −1.29 V (vs SHE) assigned to the [Ru₃O]^{−1/0/+1/+2/+3} and to the bpy^0/−1 redox processes; also a wave is observed at 0.96 V, assigned to the Ru^+2/+3 pair. Despite the conjugated BPE bridge, the electrochemical and spectroelectrochemical results indicate only a weak coupling through the π-system, and preliminary photophysical essays showed the compound decomposes under visible light irradiation.