Zur herstellung und reaktivität von bis(trimethylsilyl)dilithiomethan

At −90°C in THF or similar media bis(trimethylsilyl)dichloromethane 2 reacts with lithium-4,4′-di-tert-butylbiphenyl (LiDBB) or suspensions of freshly sublimed lithium to give the title compound 1 that can bind two equivalents of various electrophiles. 1 has a great propensity for proton abstraction and it is markedly less reactive towards ethyl iodide than (Me₃Si)2EtCLi6.     

Titration von Zink mit Kaliumhexacyanoferrat(II) bis zur maximalen Trübung

Analytical and Bioanalytical Chemistry - Zink kann in Abwesenheit von Eisen mit Kaliumferrocyanid mit Hilfe eines photoelektrischen Colorimeters bis zur maximalen Trübung titriert werden....     

Octahedral bis(acetylide) and bis(diacetylide) complexes of ruthenium(II) with linear C2MC2 and C4MC4 chains: The first X-ray structures of the all trans bis(acetylides) Ru(CO)2(CCPh)2(PEt3)2 and Ru(CO)2(CCH)2(PEt3)2

Bis(acetylides) and bis(diacetylides) of ruthenium(II), trans-Ru(CO)₂(PEt₃)₂(CCR)₂ (1) (1a, R  Ph; 1b, R  ^tBu; 1c, R  SiMe₃; 1d, R  H) and trans-Ru(CO)₂(PEt₃)₂(CCC CR)₂ (2) (2a, R  SiMe₃; 2b, R  H) have been synthesized and characterised. The first single crystal X-ray analyses of these all trans-acetylides have revealed linear C₂RuC₂ chains in 1a and 1d.     

Die Wärmeleitfähigkeit von Polyäthylen im Temperaturbereich von 20 bis 200 °C

Zusammenfassung Die W?rmeleitf?higkeit von je einemPhillips-,Ziegler- und Hochdruckpoly?thylen mit hohem Molekulargewicht wurde im Temperaturbereich von 20 bis 200 ‡C gemessen. Von 20 ‡C bis zum Schmelzende zeigt sich bei den verschiedenen Poly?thylentypen ein um so gr?\erer Abfall der W?rmeleitf?higkeit, je h?her der Kristallisationsgrad bei 20 ‡C ist. Die W?rmeleitf?higkeit in der Schmelze betr?gt etwa 6 · 10⁻⁴ cal/‡C cm sec und steigt schwach mit der Temperatur an.

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Summary Thermal conductivity of three representative types of polyethylene —Phillips-, Ziegler- and high pressure-type — has been determined from 20 to 200 ‡C. The stationary method applied in this work limited the experiments to polyethylene with extremely high molecular weight. The decrease of thermal conductivity between 20 ‡C and the melting point is an increasing function of cristallinity at 20 ‡C, whereas in the liquid phase the value of about 6 · 10⁻⁴ cal/‡C cm sec is nearly the same for each of the three investigated substances; a slight increase with temperature can be observed.

     

IR- und 1H-NMR-spektroskopische kriterien für die konfigurations-bestimmung von bis(phenyl)platin(II)-verbindungen

We describe the IR- and ¹H-NMR-spectroscopic criteria for determining the configuration in para-substituted cis- and trans-bis(phenyl)bis(tri-n-butylphosphine)platinum(II) compounds.     

QuasistationÄre Messung der WÄrmeleitfÄhigkeit von Kunststoffen im Temperatur-bereich von −180 ‡C bis +90 ‡C

Zusammenfassung Die W?rmeleitf?higkeit einiger thermoplastischer Kunststoffe wurde im Temperaturbereich von −180 ‡C bis +90 ‡C nach einem quasistation?ren Verfahren gemessen. Eine geringfügige Zunahme der W?rmeleitf?higkeit mit wachsender Temperatur wurde bei HartPolyvinylchlorid, Polytetrafluor?thylen, Polychlortrifluor?thylen und Poly?thylenterephthalat gefunden. Bei Polytetrafluor?thylen wurde bei +20 ‡C eine Stufe in der W?rmeleitf?higkeit festgestellt. Die Stufe wird der Umwandlung monoklin-hexagonal im kristallinen Anteil des Polytetrafluor?thylens zugeordnet. Messungen an zwei Poly?thylenterephthalatproben verschiedener Dichte und damit verschiedener Kristallinit?t ergaben für die Probe mit der h?heren Dichte eine gr?\ere W?rmeleitf?higkeit als für die Probe geringerer Dichte. In ?hnlicher Weise ergibt sich bei dem h?her kristallinen Niederdruckpoly?thylen eine gr?\ere W?rmeleitf?higkeit als bei dem weniger kristallinen Hochdruckpoly?thylen. Bei Niederdruckpoly?thylen und oberhalb −50 ‡C auch bei Hochdruckpoly?thylen nimmt die W?rmeleitf?higkeit im Gegensatz zu dem Temperaturverhalten der oben genannten Substanzen mit wachsender Temperatur ab.     

Cyclic bis(β-diketonate)- and bis(β-ketoesterate)-bridged titanium and zirconium alkoxide derivatives

Reaction of Ti(OiPr)(4) with various bis(β-diketones) and bis(β-ketoesters) (LH(2)) results in the formation of dimeric complexes [Ti(OiPr)(2)L](2), where each metal centre is coordinated by two terminal OiPr ligands and two bridging β-diketonate or β-ketoesterate groups (L). Macrocycles containing two M(OiPr)(2) moieties are thus formed. Reaction of Zr(OiPr)(4) with the same bis(β-diketones) and bis(β-ketoesters) results in different compounds, depending on the organic spacer connecting the two functional groups. With shorter spacers, the compounds [ZrL(OiPr)(2)](2)·2iPrOH are obtained, with the same structures as the corresponding titanium complexes. With longer spacers, however, complexes with a higher degree of substitution are formed, such as (ZrL(2))(2) and Zr(2)L(3)(OiPr)(2)·2iPrOH. The molecular weight and structure of all compounds was elucidated by ESI-MS. MS/MS of the corresponding [M+Na](+) precursor ions confirmed the proposed structures based on structure-specific product ions. Solution NMR experiments and DFT calculations additionally supported the proposed structures.     

Crystal structure of bis(α,α′-dithio-bis(formamidinium)) bis(μ2-chloro)hexachlorodimercurate(II)

The crystal and molecular structure of bis(α,α′-dithio-bis(formamidinium)) bis(μ₂-chloro)hexachlorodimercurate(II) C₄H₁₆Hg₂Cl₈N₈S₄ (I), where α,α′-dithio-bis(formamidine) is C₂H₆N₄S₂, was solved. Crystals are monoclinic, a = 8.6417(6) Å, b = 14.648(1) Å, c = 10.2111(8) Å, β = 104.949(1)°, V = 1248.8(2) ų, space group P2₁/n, Z = 4. The crystal structure is built of HgCl ₄ ^2? ions linked via inversion centers into [Hg₂Cl₈]^4? pairs and C₂H₈N₄S ₂ ²⁺ cations. [Hg₂Cl₈]^4? anions and C₂H₈N₄S ₂ ²⁺ cations form alternating layers linked by N-H…Cl hydrogen bonds into a framework structure.     

Bis(1,8-naphthylimides) and bis(1′,8′-naphthoylene-1,2-benzimidazoles) based on new bis(naphthalic anhydrides)

The reaction of bis(naphthalic anhydrides) with aniline and o-phenylenediamine under conditions of hightemperature cyclocondensation in m-cresol in the presence of a catalyst (benzoic acid) gives bis(1,8-naphthylimides) and bis(1,8-naphthoylene-1,2-benzimidazoles) which model the elementary units of polyimides and polynaphthoylenebenzimidazoles, respectively.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 649–652, May, 1991.     

Synthesis and crystal structures of bis(cyclopentyl)gallium phenoxide dimer and bis (cyclopentyl) gallium naphthoxide dimer

Tricyclopentylgallium reacted with phenol, naphthol respectively to yield phenox-ide (or naphthoxide) of biscyclopentylgallium which have been characterized by elemental analysis, IR, 1H NMR and mass spectrometry. X-ray diffraction analysis of compound 1 indicated that it belongs to the monoclinic system, space groups P21/c, with cell constants 0=9.602(3), 6=14.365(7), c=11.256(4)A, and β=97.54(3)°, Z=2(dimers), R=0.0706. Compound 2 assigned to the triclinic system, space groups P1 with cell constants a=9.392(4), 6=9.928(7), c=11.263(7) A, a=112.48(5), β=104.74(4), γ=99.95(5)°, and Z=l(dimers), R=0.0526. The molecule of 1 or 2 contains an oxygen-bridged coplanar Ga2O2 four-membered ring respectively.     

The first complex of C60 fullerene with bis(ethylenedithio)tetrathiafulvalene radical cation: C60·(BEDT-TTF·I3)

The complex of C₆₀ fullerene containing the radical cation of the organic donor,viz., C₆₀·(BEDT-TTF·I₃), where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene, was synthesized for the first time. Single crystals of the complex were grown in benzonitrile. The crystals of this compound belong to the monoclinic system with a base-centered lattice. The unit cell parameters are as follows:a=17.419(6),b=9.997(4),c=13.499(1) Å, β=99.00 (1)^o. The IR and electronic spectra of single crystals of the complex have absorption bands characteristic of the BEDT-TTF^.+ radical cation and neutral C₆₀. The ESR spectrum has a signal withg=2.0074 and δH _pp=23 G belonging to BEDT-TTF^.+. The position of the 13d_5/2 peak in the X-ray photoelectron spectrum confirms the formation of the I₃ ^? anion.     

Struktur von [CPRu(C0)2]2 (Cp  η5-pentamethylcyclopentadienyl)

The molecular structure of di-μ-carbonyl-bis[carbonyl(η⁵-pentamethylcyclopentadienyl)ruthenium] (RuRu) has been determined by a single-crystal X-ray diffraction study (monoclinic, space group P2₁/n,a  979.90(9), b = 831.91(7), c = 1427.75(12) pm, β = 100.026(9)°, R = 0.018). In the solid state the complex exists solely as the trans-carbonyl bridged isomer. The RuRu bond length is 275.2(1) pm.     

Unusual supramolecular donor—acceptor complexes of bis(crown)stilbenes and bis(crown)azobenzene with viologen analogs

The results of the comprehensive study of novel supramolecular donor-acceptor complexes of bis(crown)stilbenes and bis(crown)azobenzene with viologen analogs are generalized. The original methodology for self-assembling of the organic donor-acceptor complexes possessing a very high thermodynamic stability is described. The hydrogen bonds between the peripheral fragments of the donor and acceptor play the key role in the self-assembling. The influence of different structural factors on the thermodynamic stability of the supramolecular donor-acceptor complexes and the efficiency of charge-transfer interactions between the donor and acceptor are discussed. The driving forces of the reaction leading to exotic trimolecular charge-transfer complexes are considered. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 779–787, April, 2008.     

Synthesis and crystal structure of bis[(18-crown-6)potassium] bis(μ2-bromo)tetrabromodicopper(II)

A new complex bis[(18-crown-6)potassium] bis(μ₂-bromo)tetrabromodicopper(II), [{K(18-crown-6)}₂Cu₂Br₆] (I), is synthesized and studied by X-ray diffraction analysis (space group P2₁/n, a = 9.137 Å, b = 34.860 Å, c = 13.414 Å, β = 99.53°, Z = 4). The structure is solved by a direct method and refined by the fullmatrix least-squares method in the anisotropic approximation to R = 0.083 for 5850 independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). Complex molecule I consists of the central binuclear anion [Cu₂Br₆]^2? and two peripheral cations K(18-crown-6)]⁺ of the host-guest type bound to the [Cu₂Br₆]^2? anion through two and one K-Br coordination bonds. In the [Cu₂Br₆]^2? anion, the coordination polyhedra of two Cu atoms can be described as strongly flattened tetrahedra. In two [K(18-crown-6)]⁺ fragments, the coordination polyhedra of their K⁺ cations (coordination numbers 8 and 7) are distorted hexagonal pyramids with a base of six O atoms of the 18-crown-6 ligand and a bifurcated or ordinary vertex: the Br atoms of the [Cu₂Br₆]^2? anion. Two 18-crown-6 ligands have a standard crown conformation.     

EPR on bis(1,2-dithiosquarato)cuprate(II) in the bis(1,2-dithiosquarato)nickelate(II) host lattice — structure and spectroscopy‡

EPR spectroscopy is a well suited analytical tool to monitor the electronic situation around paramagnetic metal centres as copper(II) and therefore the structural influences on the paramagnetic ion. 1,2-Dithiosquaratometalates are available by direct synthesis from metal salts with dipotassium-1,2-dithiosquarate and the appropriate counter cations. Synthesis and characterisation of bis(benzyltributylammonium)1,2-dithiosquaratonickelate(II), (BzlBu₃N)₂[Ni(dtsq)₂], and bis(benzyltributylammonium)1,2-dithiosquaratocuprate(II), (BzlBu₃N)₂[Cu(dtsq)₂], with benzyltributylammonium as the counter ion is reported and the X-ray structures of two complexes, (BzlBu₃N)₂[Ni(dtsq)₂] and (BzlBu₃N)₂[Cu(dtsq)₂], are presented. Both complexes, crystallising in the monoclinic space group P2₁/c, are isostructural with only small differences in the coordination sphere due to the different metal ions. The diamagnetic nickel complex is therefore well suited as a host lattice for the paramagnetic Cu(II) complex to measure EPR for additional structural information.     

Asymmetric glyoxylate-ene reaction catalyzed by C2-symmetric chiral bis(oxazoline)–lanthanide complexes

Efficient C₂-symmetric chiral bis(oxazoline)-lanthanide catalysts are developed for the glyoxylate-ene reaction to afford the α-hydroxy esters in 85% yield and up to 54% ee. An enhanced level of diastereoselectivity (81% de) was obtained in the reaction between menthyl glyoxylate and alkenes catalyzed by bis(oxazoline)–Ln(OTf)₃ complex.