7791-12-0Relevant academic research and scientific papers
Kinetics of Thallium Dissolution in Aqueous Solutions of Hydrochloric Acid
Sarbaeva,Tuleshova, E. Zh.,Zhylysbaeva,Sarbaeva
, p. 1817 - 1821 (2019/09/06)
Abstract: Potentiometry is used to study the kinetics of electrochemical oxidation and reduction of thallium in aqueous solutions of hydrochloric acid. Kinetic parameters are calculated to characterize the mechanism of the electro-oxidation of thallium: c
Binding of Gold(III) from Solutions with Thallium(I) Dibutyldithiocarbamate: Synthesis, Supramolecular Self-Organization, and Thermal Behavior of the Complex ([Au{S2CN(C4H9)2}2][TlCl4])n
Ivanov,Bredyuk,Loseva
, p. 1470 - 1477 (2018/09/11)
The binding of gold(III) from solution in a 2 M HCl with thallium(I) dibutyl dithiocarbamate leads to the formation of ion-polymeric complex ([Au{S2CN(C4H9)2}2][TlCl4])n, which was studied by (13С, 15N) MAS NMR spectroscopy and X-ray diffraction analysis. In the complex comprising the nonequivalent cations [Au{S2CN(C4H9)2}2]+ (A and B) and anions [TlCl4]–, the supramolecular self-assembly is provided by secondary bonds Au···S and S···Cl. The former are involved in the formation of isomeric binuclear cations [А···А] and [В···В] that build the (···[А···А]···[В···В]···)n polymeric chain; the latter selectively combine the thallium(III) anions and the dimeric cations. Thermolysis of the complex is accompanied by gold recovery and release of TlCl.
First-principles band-structure calculations and X-ray photoelectron spectroscopy studies of the electronic structure of TlPb2Cl 5
Khyzhun,Bekenev,Denysyuk,Parasyuk,Fedorchuk
, p. 802 - 809 (2013/11/06)
We report on first-principles calculations of total and partial densities of states of atoms constituting TlPb2Cl5 using the full potential linearized augmented plane wave (FP-LAPW) method. The calculations reveal that the valence band of TlPb2Cl5 is dominated by contributions of the Cl 3p-like states, which contribute mainly at the top of the valence band with also significant contributions throughout the whole valence-band region. In addition, the bottom of the conduction band of TlPb 2Cl5 is composed mainly of contributions of the unoccupied Pb 6p-like states. Our FP-LAPW data indicate that the TlPb2Cl 5 compound is an indirect-gap material with band gap of 3.42 eV. The X-ray photoelectron core-level and valence-band spectra for pristine and Ar + ion-irradiated surfaces of a TlPb2Cl5 polycrystalline sample were measured. The measurements reveal high chemical stability and confirm experimentally the low hygroscopicity of TlPb 2Cl5 surface.
Raman spectroscopy study of products of reactions of zirconium and hafnium tetrachlorides with indium and thallium monochlorides
Salyulev,Vovkotrub
, p. 687 - 690 (2013/07/26)
Reactions of ZrCl4 and HfCl4 with InCl and TlCl accompanied by formation of several solid complex compounds were studied by the Raman spectroscopy method.
Insertion of allenes into the Pd-C bond of ortho-palladated primary arylamines of biological relevance: Phenethylamine, phentermine, (l)-Phenylalanine methyl ester, and (l)-tryptophan methyl ester. Synthesis of tetrahydro-3-benzazepines and their salts
Garcia-Lopez, Jose-Antonio,Saura-Llamas, Isabel,McGrady, John E.,Bautista, Delia,Vicente, Jose
, p. 8333 - 8347 (2013/02/22)
The previously reported ortho-metalated complexes [Pd(C,N-ArCH 2CRR'NH2-2)(μ-X)]2 derived from phenethylamine (Ar = C6H4, R = R' = H, X = Cl, Br), phentermine (Ar = C6H4, R = R' = Me, X = Cl), (l)-phenylalanine methyl ester (Ar = C6H4, R = H, R' = CO2Me, X = Cl, Br)), and (l)-tryptophan methyl ester (Ar = C 8H5N, R = H, R' = CO2Me, X = Cl) react with various allenes to give (1) the corresponding η3-allyl complexes derived from the insertion of one molecule of the allene into the Pd-C bond, the formation of which has been studied by DFT using a model complex, or (2) Pd(0) and the tetrahydro-3-benzazepinium salts, resulting from the decomposition of the above mentioned η3-allyl complexes, containing an exocyclic double bond, which, subsequently, react with a base to afford the corresponding benzazepines. The regiochemistry of these decomposition reactions has been studied and compared with that described for similar processes involving five-membered palladacycles. The crystal structures of the salts of some benzazepines and one isoquinoline, derived from a five-membered palladacycle, have been determined by X-ray diffraction studies.
Syntheses, dynamic behaviour and theoretical studies of [(Piperidinomethyl)silyl]methyl-cyclopalladated dimetallic complexes
Colquhoun, Victoria P.,Schildbach, Daniel,Martin-Romo, Raquel,Strohmann, Carsten,Villafane, Fernando
, p. 3427 - 3434 (2012/09/08)
The cationic complex [Pd{CH2SiPh2(CH 2NC5H10)-κ2C,N}(NCMe) 2]BF4 (CH2NC5H10 = piperidinomethyl) is obtained from the reaction of [Pd{CH2SiPh 2(CH2NC5H10)-κ2C,N} (μ-Cl)]2 with TlBF4 in the presence of NCMe. It reacts with KO2CCH3 leading to the dimetallic complex [Pd{CH 2SiPh2(CH2NC5H10)- κ2C,N}(μ-O2CCH3-κO:κ'O)] 2, which exists only as the transoid isomer in solution. A dynamic process due to inversion of the acetato bridges is detected by variable-temperature 1H NMR spectroscopy. The reaction of the same parent complex with Kdmpz (dmpz = dimethylpyrazolate) leads to the dinuclear complex [Pd{CH2SiPh2(CH2NC5H 10)-κ2C,N}(μ-dmpz-κN:κ'N)] 2, which in solution exists as a mixture of cisoid and transoid isomers, but no inversion of the bridging pyrazolato groups has been observed. The reaction between equimolar amounts of these two complexes in CH 2Cl2 affords low yields of the expected mixed acetato/pyrazolato-bridged complex [Pd2{CH2SiPh 2(CH2NC5H10)-κ2C,N} 2(μ-O2CCH3-κO:κ'O)(μ-dmpz- κN:κ'N)]. The mixed chlorido-pyrazolato-bridged complex [Pd 2{CH2SiPh2(CH2NC5H 10)-κ2C,N}2(μ-Cl)(μ-dmpz-κN: κ'N)] is obtained by mixing equimolar amounts of the parent dichlorido- and bis(dimethylpyrazolato)-bridged dinuclear complexes, and exhibits a dynamic process in solution corresponding to the inversion of the bridges. Only the cisoid isomers are detected for both dimetallic complexes with mixed bridging ligands. The experimental findings of the preferred transoid or cisoid structure in these dinuclear Pd complexes were supported by quantum chemical calculations. The nature of the bridging ligands determines both the presence of transoid or cisoid isomers and the rigidity in solution of dimetallic complexes containing palladacycles with the [(piperidinomethyl)silyl]methyl ligand. Copyright
Phase equilibria and some properties of solid solutions in the Tl 5Te3-Tl9BiTe6-Tl5Te 2Cl system
Babanly,Askerova,Aliev,Babanly
, p. 1833 - 1838 (2012/01/31)
Phase equilibria in the Tl5Te3-Tl9BiTe6- Tl5Te2Cl system were studied by differential thermal analysis (DTA), X-ray powder diffraction, and measurements of microhardness and also emf of concentration circuits with reference to a thallium electrode. A number of polythermal sections, the isothermal sections of the phase diagram at 760 and 800 K, and projections of the liquidus and solidus surfaces were constructed. It was shown that the system is characterized by the formation of unlimited solid solutions with the Tl5Te3 structure. The concentration dependences of the crystal lattice parameters, microhardness, and emf in the solid solutions were described.
Phase equilibria in the Tl-TlCl-Te system and thermodynamic properties of the compound Tl5Te2Cl
Babanly,Aliev,Dhafarli,Babanly
, p. 442 - 449 (2011/08/07)
The Tl-Te-Cl system was studied in the Tl-TlCl-Te composition region by differential thermal analysis, X-ray powder diffraction, and emf and microhardness measurements. A series of polythermal sec- tions, an isothermal section at 400 K, and a projection of the liquidus surface of the phase diagram were con- structed. The ternary compound Tl5Te2Cl characterized by a wide homogeneity region and incongruent melting by a syntectic reaction at 708 K was shown to exist. This compound was found to crystallize in tetragonal lattice (space group I4/mcm) with the parameters a = 8.921 ?, c = 12.692 ?, and Z = 4. Wide phase separation regions were also found in the system, including a three-phase separation region in the Tl-TlCl-Tl2Te sub- system. Regions of primary crystallization of phases, and the types and coordinates of in-and monovariant equilibria in the T-x-y diagram were determined. From emf measurement data, the standard thermody- namic functions of formation and the standard entropy were calculated for the compound Tl5Te2Cl, as follows: =ΔG0 298 355.9 ± 1.1 kJ/mol, =ΔH0298 377.1 ± 5.0 kJ/mol, andΔS0298 = 474.1 ± 6.8 J/(mol K). Pleiades Publishing, Ltd., 2011.
Actinide metals with multiple bonds to carbon: Synthesis, characterization, and reactivity of U(IV) and Th(IV) bis(iminophosphorano)methandiide pincer carbene complexes
Ma, Guibin,Ferguson, Michael J.,McDonald, Robert,Cavell, Ronald G.
, p. 6500 - 6508 (2011/08/07)
Treatment of ThCl4(DME)2 or UCl4 with 1 equiv of dilithiumbis(iminophosphorano) methandiide, [Li2C(Ph 2P=NSiMe3)2] (1), afforded the chloro actinide carbene complexes [Cl2M(C(Ph2P=NSiMe3) 2)] (2 (M = Th) and 3 (M = U)) in situ. Stable PCP metal-carbene complexes [Cp2Th(C(Ph2P=NSiMe3)2)] (4), [Cp2U(C(Ph2P=NSiMe3)2)] (5), [TpTh(C(Ph2P=NSiMe3)2)Cl] (6), and [TpU(C(Ph2P=NSiMe3)2)Cl] (7) were generated from 2 or 3 by further reaction with 2 equiv of thallium(I) cyclopentadienide (CpTl) in THF to yield 4 or 5 or with 1 equiv of potassium hydrotris(pyrazol-1- yl) borate (TpK) also in THF to give 6 or 7, respectively. The derivative complexes were isolated, and their crystal structures were determined by X-ray diffraction. All of these U (or Th)-carbene complexes (4-7) possess a very short M (Th or U)=carbene bond with evidence for multiple bond character. Gaussian 03 DFT calculations indicate that the M=C double bond is constructed by interaction of the 5f and 6d orbitals of the actinide metal with carbene 2p orbitals of both π and σ character. Complex 3 reacted with acetonitrile or benzonitrile to cyclo-add C≡N to the U=carbon double bond, thereby forming a new C-C bond in a new chelated quadridentate ligand in the bridged dimetallic complexes (9 and 10). A single carbon-U bond is retained. The newly coordinated uranium complex dimerizes with one equivalent of unconverted 3 using two chlorides and the newly formed imine derived from the nitrile as three connecting bridges. In addition, a new crystal structure of [CpUCl 3(THF)2] (8) was determined by X-ray diffraction.
Electrophilic activation and the formation of an unusual Tl +/Cr3+ tetranuclear ion-complex adduct
Liu, Shaofeng,Peloso, Riccardo,Pattacini, Roberto,Braunstein, Pierre
, p. 7881 - 7883 (2010/10/04)
Reaction of TlPF6 with the Cr(iii) complex fac-[CrCl 3(NPN)] (NPN = bis(2-picolyl)phenyl phosphine) did not lead to precipitation of TlCl but rather to addition of the Tl+ cation to the CrCl3 moiety, which resulted in a pseudo-dimeric adduct which has an unusual tetranuclear centrosymmetric structure in the solid state.
