Die Kristallstruktur von (N,N-Diethyl-N′-benzoylselenoureato)thallium(I)

The Crystal Structure of (N,N-Diethyl-N′-benzoylselenoureato)thallium(I) . Tl(C₁₂H₁₅N₂OSe) exists in a dimeric form and crystallizes in the triclinic space group P-1. The cell parameters are a = 6.501(6), b = 9.901(7), c = 12.233(9) Å, α = 91.59(2), β = 80.11(6), γ = 85.28(5)° and Z = 2. The structure was solved with Patterson and direct methods and was refined to a final R-value of 5.30%. Two complex molecules are connected by Tl? Se bonds to form a planar four membered ring with diagonally arranged Tl and Se atoms. The considerably bended chelate rings are nearly at right angle to the central four membered ring. The Tl? Se bond lengths are 3.105(3) and 3.118(3) Å, the Tl? O bond length is 2.532(9) Å.     

ESR and solid-state natural abundance 13C CP/MAS NMR study of crystalline alkyl (R = C2H5, i-C3H7, i-C4H9, s-C4H9, and C5H11) xanthate copper(II) and thallium(I) complexes

Crystalline thallium(I) alkylxanthate complexes [Tl{S(S)COR}]_n (R = C₂H₅, i-C₃H₇, i-C₄H₉, s-C₄H₉, and C₅H₁₁) and isotope-substituted heteropolynuclear Cu(II)Tl(I) complexes [⁶³⁽⁶⁵⁾CuTl₆(S₂COR)₈] (R= i-C₄H₉ and C₅H₁₁) were obtained and studied by ESR and high-resolution solid-state ¹³C CP/MAS NMR spectroscopy. According to the ¹³C NMR data, polynuclear thallium(I) complexes contain structurally equivalent alkylxanthate ligands. The ESR study revealed the Jahn-Teller dynamic effect in Cu(II)Tl(I) complexes; the nuclei of six Tl atoms are involved in the hyperfine interaction.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 48–54.Original Russian Text Copyright © 2005 by Ivanov, Bredyuk, Antzutkin, Forsling.     

Synthesis and Solid-State Structure of 2,6-Trip2C6H3Tl (Trip=2,4,6-iPr3C6H2): A Monomeric Arylthallium(I) Compound with a Singly Coordinated Thallium Atom

A “one-legged thallium” is observed in the arylthallium(I ) compound 2,6-Trip₂C₆H₃Tl (Trip=2,4,6-iPr₃C₆H₂), which was synthesized from the corresponding organolithium compound and thallium chloride. X-ray structure analysis reveals that 2,6-Trip₂C₆H₃Tl is monomeric in the solid state and contains a singly coordinated thallium atom (see space-filling model on the right).     

Crystal structure of thallium(I) 2-thiobarbiturate

The crystal and molecular structures of thallium(I) thiobarbiturate C₄H₃N₂O₂STl (C₄H₄N₂O₂S is 2-thiobarbituric acid, Н₂ТВА) have been determined. Crystallographic data for Tl(НТВА) are a = 11.2414(7) Å, b = 3.8444(3) Å, с = 14.8381(9) Å, β = 99.452(2)°, V = 649.00(7) ų, space group P2/с, Z = 4. Each of the two independent thallium ions is bonded to four oxygen and two sulfur atoms to form a distorted tetrahedron. N?H…O and C?H…S hydrogen bonds form a branched three-dimensional network. The structure is also stabilized by π?π interaction between heterocyclic НТВА^- ions. The IR spectra of Tl(НТВА) agree with X-ray powder diffraction data. The compound is also stable below 280°C, and Tl₂SO₄ is one of the thermolysis products in an oxidative medium in the region of 500?650°C.     

The structure of di-μ-pentafluorobenzoatobis[bis(pentafluorophenyl)(triphenylphosphine oxide)thallium(iii)]

An X-ray crystallographic study has shown that the complex (C₆H₅)₂TlO₂CC₆F₅(OPPh₃) has a dimeric structure with unsymmetrical pentafluorobenzoate bridging (TlO 2.531 and 2.789 Å) but an exact crystallographic centre of symmetry. The pentafluorobenzoate groups are also unsymmetrically chelated to thallium (TlO 2.389 and 2.531 Å.), which overall has irregular six coordination.     

(Chloromethyl)thallium(III) compounds

Aryl(chloromethyl)thallium chlorides, Ar(ClCH₂)TlCl (Ar=C₆H₅, p-CH₃C₆H₄) have been prepared by treatment of arylthallium dichlorides with diazomethane. The derived carboxylates, Ar(ClCH₂)TlX, react with HgX₂ to give the dicarboxylates, (ClCH₂)TlX₂ (X = OCOCH₃, OCOC₃H₇-i) and with tetramethyltin to give CH₃(ClCH₂)TlX compounds. R(ClCH₂)TIX compounds (R = CH₃, C₆H₅, p-CH₃C₆H₄) undergo disproportionation in methanol to R₂TlX and (ClCH₂)₂TlX compounds.     

Die Kristallstruktur von p-Tolylbis(diethyldithiocarbamato)-thallium(III) und Phenylbis(methylxanthogenato)bismut(III)

Crystal Structure of p-Tolylbis (diethyldithiocarbamato)thallium(III) and Phenylbis-(methylxanthogenato)bismut(III) The crystal structure of 4-CH₃(C₆H₄)? Tl(S₂CN(C₂H₅)₂)₂ (P2₁/c, a = 11.973(3), b = 10.692(3), c = 19.232(4) Å, β = 114.02(2)°, Z = 4) and C₆H₅-Bi(S₂COCH₃)₂ (P2₁/c, a = 6.395(2), b = 24.684(8), c = 9.732(3) Å, β = 101.38(3)°, Z = 4) was solved from X-ray diffraction data of single crystals. From the interatomic distances follows that the dithiocarbamate and xanthogenate ligands coordinate asymmetrically bidentate to the metal as presumed and exclusively through the sulfur atoms. Differences in the coordination sphere of bismut and thallium give evidence for a “stereochemically active lone pair” on the bismut atom.     

The trigonal–bipyramidal triiodo­thallium(III) complex [TlI3{(CH3)2SO}2]

The title compound, bis(dimethyl sulfoxide)triiodo­thallium(III), [TlI₃(C₂H₆OS)₂], was crystallized from equimolar amounts of Tl^II and I₂ in a dimethyl sulfoxide (DMSO) solution. After the initial redox reaction, the thallium(III)–iodo complex forms and precipitates as a DMSO solvate. In the crystal structure, Tl is surrounded by three iodide ligands in the equatorial plane and two O‐coordinated DMSO mol­ecules in the axial positions, forming a slightly distorted trigonal bipyramid. The complex lies on a twofold rotation axis, making the DMSO mol­ecules and two of the I atoms crystallographically equivalent.     

Schwermetall-π-Komplexe. X. Synthese und Kristallstruktur von {[(1,3,5-(CH3)3C6H3)2Tl][AlCl4]}2: ein arenstabilisiertes dimeres Thallium(I)-tetrachloroaluminat

π-Complexes of Heavy Metals. X. Synthesis and Crystal Structure of {[(1,3,5-(CH₃)₃C₆H₃)₂Tl][AlCl₄]}₂: an Arene Stabilized Dimeric Thallium(I) Tetrachloroaluminate From a solution of AlCl₃ and TlCl in mesitylene, the bis(arene)thallium complex {[(1,3,5-(CH₃)₃C₆H₃)₂Tl][AlCl₄]}₂ ( 1 ) (space group P2₁/c with a = 19.575(4) Å, b = 12.436(2) Å, c = 19.415(4) Å, β = 101.69(3)° at T = ?90 ± 1°C; Z = 4) will crystallize at low temperature. This compound can be described as a dimeric thallium(I) tetrachloroaluminate with a sceleton similar to that of (TeI₄)₄, shielded by four arenes, in pairs coordinated at the thallium atoms. In the solid state the complete configuration has point group symmetry 1 (C₁). Tl? Cl distances ranging from 3.292(3) to 3.679(3) Å point out an ionic bonding situation between arene₂Tl⁺ and AlCl₄^? fragments. The strengths of the η⁶ like Tl-arene interactions are characterized by distances Tl(1)–C of 3.250 Å and 3.315 Å, and Tl(2)? C of 3.285 Å and 3.328 Å and a temperature of release of all arene molecules of 61°C, which has been determined by differential thermal analysis, to yield pure thallium(I) tetrachloroaluminate.     

Highly polyhapto-aromatic interactions in thallium(I) coordination

In the solid state, the Tl(I) complex of 4-hydroxybenzoate (HB⁻), [Tl(HB)]_n (1), can be regarded as containing polymeric chains linked through 2 × η⁶ interactions of the Tl atoms with phenyl groups from adjacent units. The thallium atoms contain close Tl^I ? π (aromatic) contacts, thus attaining a total hapticity of 16 with environments TlO₄C₁₂. The unusually high coordination number in the this compound may reflect the capacity of Tl(I) to act as both a Lewis acid and a Lewis base.     

Thallates of alkali metals and monovalent thallium formed in aqueous solutions of their hydroxides

Conclusions As a result of an investigation of the heterogeneous equilibria in M₂O-Tl₂O₃-H₂O systems, where M=Tl(I), Li, Na, K, Rb, and Cs, at 25°C it was established that the components only react in systems with thallium(I) and sodium hydroxides with the formation of thallium(I) orthothallate and restricted solid solutions between thallium oxide and the orthothallate based on thallium oxide and sodium hydroxythallate Na₃Tl(OH)₆, respectively.At elevated temperatures of 150 and 200°C it was established that potassium metathallate is formed in the K₂O-Tl₂O₃-H₂O system while sodium metathallate NaTlO₂ and a hydrated thallate of the composition 4Na₂O·Tl₂O₃·(3–4)H₂O are formed in the Na₂O-Tl₂O₃-H₂O system at 150°C. The thallates Tl₃TlO₃, Na₃Tl(OH)₆, NaTlO₂, and KTlO₂ have been isolated in a pure form and identified.The amphoteric nature of thallium oxide has been proven.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1689–1693, August, 1984.     

Structure of palladium quinoline-8-selenolate Pd(C9H6NSe)2

The molecular and crystal structure of palladium quinoline-8-selenolate Pd(C₉H₆NSe)₂ has been determined by X-ray structural analysis. The structures of the five-membered metallocycles of palladium 8-hydroxy-, 8-mercapto-, and 8-hydroselenoquinolinates of one type are compared. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 396–402, March, 2006.     

Kinetics of the oxidation of cyclohexene by thallium(III) acetate

The kinetics of the reaction by which thallium(III) acetate oxidizes cyclohexene in glacial acetic acid medium, has been studied by UV spectrophotometric observation at 30°C. The consumption of thallium(III) acetate follows a second-order rate law exhibiting first-order dependence on each of thallium(III) acetate and cyclohexene; however, the first-order dependence on cyclohexene disappears at high cyclohexene concentrations as pseudo-first-order conditions prevail above 0.2 M cyclohexene. A steady-state model of the following form is proposed: where Tl, Cy, and Com are units of Thallium(III) acetate, cyclohexene, and a reaction complex. The value of k₂ has been evaluated as 0.00027 and (k_?1 + k₂) as 0.0385k₁. For low thallium(III) acetate concentrations the reaction kinetics follow the rate law: where α = the excess concentration of cyclohexene over thallium(III) triacetate. For thallium(III) acetate concentrations above 0.02 M, double salt formation of thallium(III) acetate with product thallium(I) acetate removes thallium(III) acetate from the reaction and a modified rate law is observed. Runge–Kutta numerical solutions to the differential equations provide confirmation that the rate expressions are valid in predicting the observed concentrations of thallium(III) acetate.     

Crystal structure of dimethylgold(III) 8-hydroxyquinolinate and 8-mercaptoquinolinate

A crystal-chemical study of dimethylgold(III) complexes with 8-hydroxyquinoline (CH₃)₂Au(OR) and 8-mercaptoquinoline (CH₃)₂Au(SR) (R = C₉H₆N) was performed. Crystal data for (CH₃)₂Au(OR): a = 8.7133(17) Å, b = 27.875(6) Å, c = 8.6688(17) Å, β = 102.76(3)°, Z = 8, ρ(calc) = 2.401 g/cm³, space group P2₁/c, R = 0.0909; for (CH₃)₂Au(SR): a = 3.5401(7) Å, b = 15.689(3) Å, c = 19.910(4) Å, β = 99.81(3)°, Z = 4, ρ(calc) = 2.361 g/cm³, space group P2₁/c, R = 0.0712. Both structures are molecular and involve neutral (CH₃)₂Au(L) molecules, L = C₉H₆NO or C₉H₆NS. In the structures, the molecules are arranged in stacks joined by van der Waals interactions. The average Au…Au intrastack distances are 3.57 Å and 4.34 Å for (CH₃)₂Au(OR) and 3.5 Å for (CH₃)₂Au(SR).     

Syntheses and characterization of thallium(I) complexes with 3-nitrophenoxide [Tl(3-np)], 4-nitrobenzoate [Tl(4-nb)] and 2,4-dinitrophenoxide [Tl(2,4-dnp)]: X-ray crystal structures of [Tl(3-np)]n and Tl(2,4-dnp) (two new polymeric compounds)

Complexes thallium(I)3-nitrophenoxide [Tl(3-np)], thallium(I)2,4-dinitrophenoxide [Tl(2,4-dnp)] and thallium(I)4-nitrobenzoate [Tl(4-nb)] have been synthesized using a direct reaction between TlNO₃ and the appropriate ligand. The complexes have been isolated and characterized by IR spectra and CHN elemental analyses. The structures of [Tl(3-np)]_n and [Tl(2,4-dnp)] have been confirmed by X-ray crystallography. The single crystal X-ray crystallography of [Tl(3-np)]_n shows the complex to be a one-dimensional polymer as a result of bridging 3-nitrophenoxide ligands. The Tl atoms have an unsymmetrical three-coordinate, O₃ geometry (three oxygen atoms of the 3-nitrophenoxide ligand). The crystal structure of [Tl(2,4-dnp)] shows the complex to be a three-dimensional polymer as a result of bridging 2,4-dinitrophenoxide ligands. The Tl atoms have an unsymmetrical two-coordinate, O₂ geometry (two oxygen atoms of the 2,4-dinitrophenoxide ligand). The arrangement of the 3-nitrophenoxide and 2,4-dinitrophenoxide ligands suggests a gap in coordination geometry around the Tl(I) ions, occupied possibly by a stereoactive lone pair of electrons on Tl(I). There is a π–π stacking interaction between the parallel aromatic rings belonging to adjacent chains in the compounds that may help to increase the ‘gap’ in coordination geometry around the Tl(I) ions.     

1H NMR Spectra of Phenylthallium (III) Crown-Ether Complexes, [C6H5Tl (III)(Crown)X]n(ClO4) (n=1 OR 2); Trans Influence of The X Groups

Abstract

Trans influence of the X groups on the spin-pin coupling constants between the thallium nucleus and the meta protons of the phenyl group attached to the thallium atom, J(Tl-H^m), were studied for a number of phenylthallium (III) crown-ether complexes, [C₆H₅Tl (III) (crown)X]n(ClO₄) (n=1 or 2).     

Synthesis and structure of di(2-phenyl-8-quinolyl) diselenide and zinc bis[(2-phenyl-8-quinolyl)selenolate]

Di(2-phenyl-8-quinolyl) diselenide [2-(C₆H₅)C₉H₅NSe]₂ and zinc bis[(2-phenyl-9-quinolyl)selenolate], Zn [2-(C₆H₅)C₉H₅NSe]₂, have been synthesized. The molecular and crystal structure of the compounds were determined by X-ray structural analysis. The structures of the 2-phenyl-8-quinolylselenol ligand in the molecules of di(2-phenyl-8-quinolyl) diselenide and in the intracomplex compound of zinc are compared. The effect of the phenyl group in position 2 of the quinoline nucleus on the formation of the molecules and their packing in the crystal structure is discussed.     

Darstellung und Kristallstruktur von Tris[1,3-bis(phenyltriazenido)benzol]-di-thallium(III)

Synthesis and Crystal Structure of Tris[1,3-bis(phenyltriazenido)benzene]-di-Thallium(III) Tris[1,3-bis(phenyltriazenido)benzene]-di-thallium(III) is formed by the reaction of di-sodium-1,3-bis(phenyltriazenido)benzene with thallium(I)-sulfate in a THF/H₂O mixture in the presence of oxygen. The compound crystallizes in the triclinic space group P1 1 with the lattice parameters a = 1368.8(2), b = 1539.3(2), c = 1676.0(3) pm, α = 106.04(3)°, β = 90.50(3)°, γ = 109.94(3)° and two formula units in the unit cell. The complex consists of two Tl atoms and three ligands, of which each N₃-unit acts as bidentate chelating group. The coordination sphere of Tl is trigonal prismatic with a coordination number of 6. The distances Tl? N range from 228 to 244 pm.     

Tl2D coordination polymer involving close Tl?π (aromatic) contacts, [Tl3(μ-BPC)2(μ-NO3)]n

A two-dimensional polymer, [Tl₃(μ-BPC)₂(μ-NO₃)]_n [BPC = biphenyl-2-carboxylate], has been synthesized and characterized. Its single-crystal X-ray structure shows three types of Tl^I-ions with coordination numbers of 5 (Tl1 and Tl2), and 4 (Tl3). Two of the thallium atoms, Tl1 and Tl3, contain close Tl^I?π (aromatic) contacts, thus attaining a total hapticity of 11 and 10 with environments Tl1O₅C₆ and Tl3O₄C₆, respectively.     

Reactivity of thallium tris[tris(pentafluorophenyl)germyl] mercurate

Metallic lithium and dibenzenechromium displace thallium from (R^f₃Ge)₃HgTl·1.5DME (R^f = C₆F₅, DME = 1,2-dimethoxyethane) to give (R^f₃Ge)₃HgLi·3DME and [(R^f₃Ge)₄Hg][Cr(C₆H₆)₂]₂, respectively. Reactions of thallium germylmercurate with halides of metals and organometallics in DME/EtOH solution produce ionic compounds of [(R^f₃Ge)₃Hg]^? M⁺ type, which (depending on “M”) (a) may be isolated as pure compounds, (b) disproportionate, (c) form covalent derivatives R^f₃Ge-m or (d) undergo alcoholysis. A general scheme for the reactions has been proposed.