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.     

Reaction of (C6F5)2HGeGeH(C6F5)2 with triethylbismuth: molecular structure of [(C6F5)2Ge]4Bi2

The reaction of (C₆F₅)₂HGeGeH(C₆F₅)₂ with triethylbismuth affords a new polynuclear germylbismuth derivative, [(C₆F₅Ge]₄Bi₂ (1). The metal framework of molecule1 has the form of a gable roof built by two central Bi atoms and four peripheral Ge atoms with covalent Bi-Bi bonds [3.045(3) Å], Bi-Ge [2.724(5)-2.755(4) Å] and Ge-Ge [2.444(6), 2.465(6) Å].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 921–924, May, 1994.     

Reactions of dysprosium diiodide with phenyl-and pentafluorophenylgermanium compounds

Reactions of DyI₂ with (C₆F₅)₃GeH, (C₆F₅)₃GeBr, and (C₆F₅)₂GeBr₂ gave rise to the hyperbranched polymer [(C₆F₅)₂Ge(C₆F₄)]_n (4) in 22% to 65.7 yields. The major product of the reaction with (C₆F₅)₃GeBr was perfluorinated hexaphenyldigermane in 61% yield. Under the same conditions, the germylmercury compound [(C₆F₅)₃Ge]₂Hg yielded the ionic complex { [(C₆F₅)₃Ge]₃Hg}⁻[DyI₂]⁺. Hexaphenyldigermane slowly reacted with DyI₂ even at elevated temperature to give polymer 4 in 8% yield. Perfluorinated tetraphenylgermane and nonfluorinated phenylgermanes Ph₃GeH, Ph₃GeGePh₃, and (Ph₃Ge)₂O did not react with DyI₂ but they initiated its reaction with THF. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2428–2432, November, 2005.     

Interaction of Phosphorus Iminoilides with Metal Acetates. Crystal and Molecular Structure of Cu[(2-O–)(5-NO2)C6H3N–CH=CH–+PPh3]2 · 2CHCl3

The structure of the Cu[(2-O^–)(5-NO₂)C₆H₃N–CH=CH–⁺PPh₃]₂ complex with the CuN₂O₂ coordination core of distorted square-planar geometry was established by X-ray diffraction analysis. The molecules in the crystal structure of the Cu[(2-O^–)(5-NO₂)C₆H₃N–CH=CH–⁺PPh₃]₂ · 2CHCl₃ solvate are bound via hydrogen bonds of two types, namely, C(sp ²)–H···O and C(sp ³)–H···O.     

The synthesis of some (pentafluorophenyl)germanium compounds

Tris(pentafluorophenyl)germanium bromide reacts with lithium aluminium hydride or triethylgermane to give tris(pentafluorophenyl)germane. On reaction with HgR₂ [where R = Et, Et₃Ge and (Me₃Si)₂N] or reaction with diethylcadmium, the latter gave the hitherto unknown [(C₆F₅)₃Ge]₂Hg or [(C₆F₅)₃Ge]₂Cd. The germylmercurial compound could also be prepared by reaction of metallic mercury with [(C₆F₅)₃Ge]₂Cd and by exchange of bis(triethylgermyl)mercury with (C₆F₅)₃GeBr. Some reactions of bis[tris(pentafluorophenyl)germyl]mercury are discussed.     

Formation,properties, and thermal decomposition of bisarene chromium(i) and molybdenum(i) fullerides

Fullerides [(⁶-Ph₂)₂Cr]⁺[C₆₀]^·–, [(⁶-C₁₀H₁₂)₂Cr]⁺[C₆₀]^·– (C₁₀H₁₂ is tetralin), and [(⁶-PhCH₃)₂Mo]⁺[C₆₀]^·– were synthesized. The molecular structure of [(⁶-Ph₂)₂Cr]⁺[C₆₀]^·– was established. In this compound at 100 K, radical anions C₆₀ ^–· are linked by an ordinary bond to form dimers, whereas at 293 K they are disordered and do not form dimers. The [(⁶-tetralin)₂Cr]⁺[C₆₀]^·– fulleride is stable in vacuo (10^–2 Torr) below 429 K, and [(⁶-toluene)₂Mo]⁺[C₆₀]^·– is stable below 581 K.Based on the materials presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry (Moscow, May 30–June 4, 2004) dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1973–1976, September, 2004.     

Photochemistry of Long-Lived [(CF3)2CF]2C·C2F5 Radicals in a Hexafluoropropylene Trimer Matrix

The kinetics of photodecomposition of long-lived [(CF₃)₂CF]₂C^·C₂F₅ radicals (I) in glassy and liquid hexafluoropropylene trimer was studied at 77 and 300 K, respectively. It was found that the phase state of the hexafluoropropylene trimer matrix did not affect the photodecomposition mechanism. In both cases, I eliminates ^·CF₃ radical from the perfluoroethyl fragment. The molar absorption coefficient of I was determined: ₂₅₀ = 49 m² mol^–1. It was shown that the photodecomposition of I in a liquid matrix at 300 K led to the formation of other long-lived radicals. One of these species is [(CF₃)₂CF]₃C^· radical, which results from addition of ^·CF₃ radical to the double bond of a hexafluoropropylene trimer molecule.     

X-ray structural analysis of a novel organic metal (BEDT-TTF)4[Hg2Cl6]·PhCl

X-ray structural analysis has revealed that reaction of (BEDT-TTF)[HgCl₃]^– with PhCl leads to the formation of a cation-radical salt (BEDT-TTF)₄[Hg₂Cl₆]· PhCl, which exhibits a laminar crystal structure. The cationic layer is characterized by a grid or lattice network of contracted S...S intermolecular distances (3.396(4)–3.647(5) Å), which unite the BEDT-TTF cations in ribbons or bands, parallel to the [014] direction, and which also bind the ribbons together in a direction close to the [010] axis. The presence of this type of lattice network explains the metallic nature of the conductivity of this salt (BEDT-TTF)₄Hg₂Cl₆]·PhCl in the temperature range 300.0–1.5 K, and is the basis of assigning this salt to a new class of organic, two-dimensional conductors. The [Hg₂Cl₆]^2– anions and PhCl solvent molecules are united via secondary Hg...Cl 3.176(5) Å and Cl...Cl 3.480(6) Å interaction forces to form centrosymmetric tetramers [Hg₂Cl₆PhCl]₂ ^4–, stretched out along the [014] axis direction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2062–2070, September, 1991.The authors wish to acknowledge R. N. Lyubovskaya for supplying the crystals and for helpful discussion of the results.     

The Structure of Pd2(CH≡CC6H5)2(C5H7O2)3(BF3)2BF4

IR and NMR data showed that the ionic complex Pd₂(CHCC₆H₅)₂(C₅H₇O₂)₃(BF₃)₂BF₄ isolated in the reaction Pd(Acac)₂ + PA + 5BF₃OEt₂ (Acac is C₅H₇O₂, PA is phenylacetylene) is an adduct of two complexes, namely, (Acac)PdBF₄ and [(PA)₂Pd(C³-Acac · BF₃)]⁺(Acac · BF₃)^– (coordinatively unsaturated). On dissolution in deuteroacetone or deuteromethanol, the [(Acac)PdF₂BF₂Pd(C³-Acac · BF₃)(PA)₂]⁺(Acac · BF₃)^– adduct decomposed to Pd(Acac)₂, 2BF₃ · L (L = (CD₃)₂CO, CD₃OD) and the [L(PA)₂Pd(C³-Acac]⁺BF₄ ^– complex.     

Pentafluorophenylgermylbismuth compounds

Triethylbismuth reacts with (C₆F₅)₃GeH to give (C₆F₅)₃GeBiEt₂ and [(C₆F₅)₃Ge]₂BiEt and with (C₆F₅)₂GeH₂ to give [(C₆F₅)₂GeBiEt]₂. The presence of C₆F₅ radicals does not increase the stability of

compounds (M = Ge, Sn). Their reactivity in the transmetallation reaction with mercury has been studied.     

Formation and decay of trifluoromethyl radicals during photodecomposition of the long-lived perfluoro-2,4-dimethyl-3-ethylpent-3-yl radical

UV irradiation of the long-lived radical [(CF₃)₂CF]₂C^·C₂F₅ (1) in a hexafluoropropylene trimer (HFPT) glassy matrix at 77 K and in a HFPT solution at 300 K leads to its decomposition to the ^·CF₃ radical and perfluoroolefin molecule. About 90% of the ^·CF₃ radicals formed recombine at 300 K. The remaining radicals add to the HFPT molecules generating the long-lived radicals [(CF₃)₂CF]₃C^·. Unlike the ^·CF₃ radicals produced by the photodecomposition of radicals 1, the ^·CF₃ radicals formed during radiolysis of HFPT are not stabilized in the glassy HFPT matrix at 77 K.     

New series of platinum group metal complexes bearing η- and η-cyclichydrocarbons and Schiff base derived from 2-acetylthiazole: Syntheses and structural studies

The mononuclear complexes [(η⁶-arene)Ru(ata)Cl]PF₆ {ata = 2-acetylthiazole azine; arene = C₆H₆ [(1)PF₆]; p-ⁱPrC₆H₄Me [(2)PF₆]; C₆Me₆ [(3)PF₆]}, [(η⁵-C₅Me₅)M(ata)]PF₆ {M = Rh [(4)PF₆]; Ir [(5)PF₆]} and [(η⁵-Cp)Ru(PPh₃)₂Cl] {η⁵-Cp = η⁵-C₅H₅ [(6)PF₆]; η⁵-C₅Me₅ (Cp^*) [(7)PF₆]; η⁵-C₉H₇ (indenyl); [(8)PF₆]} have been synthesised from the reaction of 2-acetylthiazole azine (ata) and the corresponding dimers [(η⁶-arene)Ru(μ-Cl)Cl]₂, [(η⁵-C₅Me₅)M(μ-Cl)Cl]₂, and [(η⁵-Cp)Ru(PPh₃)₂Cl], respectively. In addition to these complexes a hydrolysed product (9)PF₆, was isolated from complex (4)PF₆ in the process of crystallization. All these complexes are isolated as hexafluorophosphate salts and characterized by IR, NMR, mass spectrometry and UV–Vis spectroscopy. The molecular structures of [2]PF₆ and [9]PF₆ have been established by single-crystal X-ray structure analyses.     

Replacement of Trimethylamine in Trimethylamine‐trispentafluoroethyl‐borane. Structures of [(C2F5)3BNMe3], [NMe4][(C2F5)3BOH], and K[(C2F5)3BCH2(CO)C6H5]

Trimethylamine‐tris(pentafluoroethyl)borane [(C₂F₅)₃BNMe₃] ( 1 ) reacts at 190 °C with water under displacement of the trimethylamine ligand to yield the hydroxy‐tris(pentafluoroethyl)borate [(C₂F₅)₃BOH]^? ( 2 ). In tributylamine 1 reacts with alkynes HC≡CR to form novel ethynyl‐tris(pentafluoroethyl)borate anions [(C₂F₅)₃BC≡CR]^? – R = C₆H₅ ( 3 ), C₆H₄CH₃ ( 4 ), Si(CH(CH₃)₂)₃ ( 5 ) – in moderate yields. Compound 3 adds water across the triple bond to form the novel anion [(C₂F₅)₃BCH₂(CO)C₆H₅]^? ( 6 ). The structures of [(C₂F₅)₃BNMe₃], [NMe₄][(C₂F₅)₃BOH] and K[(C₂F₅)₃BCH₂(CO)C₆H₅] have been determined by x‐ray crystallography.     

Crystal and Molecular Structures of 3-Carboxypropyltriphenylphosphonium Diiodobromide

Complexation in the 3-carboxypropyltriphenylphosphonium bromide–molecular iodine system in chloroform was studied. The maximum number of iodine molecules coordinated by 3-carboxypropyltriphenylphosphonium bromide was established by the spectrophotometric method using a function of the average-iodine number, and the stability constant of the complex was determined. The [(C₆H₅)₃P(CH₂)₃COOH]BrI₂ diiodobromide was studied by X-ray diffraction analysis. The characteristic feature of the crystalline salt was the formation of dimer associates: anionic associates were formed due to the Br···Br intermolecular interactions and cationic associates were formed due to the O···H–O hydrogen bonds. The data obtained were correlated to the results of quantum-chemical calculations.     

Synthesis and structure of 1,1′-bis(pentafluorophenyl)tetrahydrodigermane

Dehydrogenation of pentafluorophenylgermane in the presence of catalytic amounts of a Wilkinson complex, certain Rh^I ortho-benzosemiquinolate complexes, or (Ph₃P)₄Pt leads to tetrahydrodigermane, C₆F₅H₂GeGeH₂C₆F₅. X-ray analysis has confirmed thetrans-arrangement of the C₆F₅-cycles at the Ge atoms. The Ge-Ge bond length is 2.394(1) Å. The doublet pattern of the band due to the Ge-H bonds (v 2090 and 2104 cm^–1) in the IR spectrum is probably associated with nonequivalence of the hydrogen atoms in the molecule.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 315–318, February, 1994.     

New routes to pentafluorophenyl derivatives with germanium-chalcogen bonds

Tris(pentafluorophenyl)germanethiol, (C₆F₅)₃GeSH (Ia), was obtained in good yield by heating the tris(pentafluorophenyl)germane with elemental sulphur or by the exchange between Et₃GeSH and (C₆F₅)₃GeBr. The reaction between sulphur and (C₆F₅)₂GeH₂ or C₆F₅GeH₃ gives heterocyclic products with chains of alternating germanium and sulphur atoms in the cycles. The compounds [(C₆F₅)₃Ge]₂X (X = S, Se) were prepared by exchange reaction of (Et₃Ge)₂X with tris(pentafluorophenyl)germanium bromide and by reaction of chalcogens (S₈, Se₈) with hexakis(pentafluorophenyl)digermane. Ia reacts with diethylmercury affording (C₆F₅)₃GeSHgEt. Insertion of elemental sulphur into the GeHg bond of bis[tris(pentafluorophenyl)germyl]mercury led to the thermally stable (C₆F₅)₃GeSHgGe(C₆F₅)₃.     

Reactivity of germylmercurate complexes

The selective insertion of sulfur into the GeHg bond in the ionic complex {[(C₆F₅)₃Ge]3Hg}⁻Cp₂Co⁺ results in the formation of mono-, di- and trithiolate derivatives. The compounds have been characterized by elementary analysis, IR, ¹⁹F and ¹⁹⁹Hg NMR spectroscopy. The molecular structure of {Hg[SGe(C₆F₅)₃]₃}⁻-Cp₂Co⁺ has been determined by X-ray analysis. Sulfur-containing complexes are donors of chalcogen atoms in the reaction with covalent and ionic polynuclear organometallic compounds. Ytterbium dicyclopentadienide and vanadocene displace cobaltocene from {[(C₆F₅)₃Ge]₃Hg}⁻-Cp₂Co⁺, and Cp₂Co removes thallium from its germylmercurate complex. A general scheme for the reaction of vanadocene with cobalticinium germylmercurate has been proposed. The zerovalent triphenylphosphine complex of platinum Pt(PPh₃)₄ destroys the ionic structure of {[(C₆F₅)₃Ge]₂HgI}⁻(C₆H₆)2Cr⁺to give dibenzenechromium iodide and a polynuclear compound with GeHgPtGe chain.     

Pentafluorophenylthiolate derivatives of ruthenium(II), rhodium(I) and palladium(II)

Summary The pentafluorophenylthiolate anion [C₆F₅S]^– reacts with chloro-bridged binuclear complexes of Ru^II, Rh^I and Pd^II to give the compounds [(N-N)(PPh₃)₂Ru(SC₆F₅)]₂Cl₂ (1) (N-N = bipyridine), [LRh(SC₆F₅)]_n (L = cycloocta-1,5-diene (2) or norbornadiene (3), n = 2 and L = dicyclopentadiene (4) for which n is probably 4), [(PPh₃)Pd(SC₆F₅)Cl]₂ (5) and (MeS-CHMeCHMeSMe)Pd(SC₆F₅), (6).¹⁹F n.m.r. spectroscopy shows a variable number of isomers depending on the compound considered.     

Inclusion Compounds of Thiourea and Paralkylated Ammonium Salts. Part VII. Hydrogen-Bonded Host Lattices Constructed from Thiourea and Anionic Species Derived from Benzoic Acid

New inclusion complexes (n-C₃H₇)₄N⁺C₆H₅CO ₂ ^– · 3(NH₂)₂CS (1), (n-C₄H₉)₄N⁺[(C₆H₅CO₂)₂H]^–·6(NH₂)₂CS (2) and (C₂H₅)₄N⁺C₆H₅CO ₂ ^– ·(NH₂)₂CS (3) have been prepared and characterized by X-ray crystallography. Crystal data, MoK radiation: 1, space group P2₁2₁2₁, Z = 4, a = 8.544(3), b = 14.588(4), c = 24.448(4) Å, and R1 = 0.062 for 1536 observed data; 2, space group Pbcn, Z = 4, a = 24.938(3), b = 8.911(1), c = 23.733(9) Å, and R1 = 0.055 for 2132 observed data; 3, space group P2₁2₁2₁, Z = 4, a = 9.996(2), b = 10.122(4), c = 18.350(2) Å, and R1 = 0.049 for 1180 observed data. In the crystal structure of 1, the (n-C₃H₇)₄N⁺ cations are stacked in a single column and accommodated within each channel built up by wide thiourea ribbons and benzoate ions via N—H···O hydrogen bonds. In the crystal structure of 2, the tetrabutylammonium cations are arranged in a zigzag column within each channel built of parallel corrugated thiourea layers that are inter-linked by dimeric [(C₆H₅CO₂)₂H]^– groups through N—H·O hydrogen bonds. In compound 3 the (C₂H₅)₄N⁺ cations are accommodated in pseudo-channels generated from infinitely extended thiourea-benzoate composite ribbons.     

Analytische Anwendung substituierter Selenoniumsalze

Zusammenfassung Es werden die Extraktions- und Fällungsreaktionen komplexer Übergangsmetall-Anionen untersucht. Durch geringe Löslichkeiten zeichnen sich u. a. das Triphenylselenonium-Dichromat, Perchlorat und -Molybdat aus (Wolframat leicht löslich). Die Verbindung [(C₆H₅)₃Se]₂ Cr₂O₇ ist quantitativ extrahierbar, [(C₆H₅)₃Se]ClO₄ eignet sich zum Nachweis von ClO₄ ^–-Mengen ab 5 g neben großen Mengen ClO₃ ^–. Die extraktiv-photometrische Bestimmung von Chrom als [(C₆H₅)₃Se]₂Cr₂O₇ ermöglicht die Ermittlung von 25 g Cr neben Mangan und Vanadium in Stählen verschiedenster Zusammensetzung. In Triphenylselenoniumverbindungen kann das Kation als [(C₆H₅)₃Se][B(C₆H₅)₄] gravimetrisch bestimmt werden.

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Summary The liquid-liquid extraction and precipitation of anionic complexes of transition metals employing selenonium salts are investigated. Triphenylselenonium dichromate, perchlorate and molybdate are advantageous because of their low solubility (the tungstate is easily soluble). [(C₆H₅)₃Se]₂Cr₂O₇ can be extracted quantitatively. [(C₆H₅)₃Se]ClO₄ is suitable for the detection of 5 g of ClO₄ ^– in presence of high quantities of ClO₃ ^–. The liquid-liquid extraction of chromium as [(C₆H₅)₃Se]₂Cr₂O₇ allows the determination of 25 g Cr in cast-iron and steels, containing manganese, vanadium and molybdenum. The cation [(C₆H₅)₃Se]⁺ in selenonium compounds can be determined by precipitation as [(C₆H₅)₃Se] [(C₆H₅)₄B].

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Herr Wolfgang Renner führte die Analysen verschiedener [TPSe]-Verbindungen durch und untersuchte die Fällungsreaktion des ClO₄ ^–. Der Deutschen Forschungsgemeinschaft gebührt besonderer Dank für die Unterstützung der Arbeit durch Sachbeihilfen.