Gas‐Phase Infrared Spectra of Three Compounds of Astrochemical Interest: Vinyl,Allenyl, and Propargyl Isocyanides

Isocyanides, isomers of the cyanides detected in the interstellar medium, are also possible components of this medium. The infrared spectra (5000–500 cm^?1) of gaseous vinyl isocyanide, allenyl isocyanide, and propargyl isocyanide have been recorded at 0.1 cm^?1 resolution. When prepared on a gram scale to produce a partial pressure of 10 mbar after evaporation in the cell, these three isocyanides, which have previously been reported to be kinetically unstable, do not display any sign of decomposition when recording the spectra. Geometry optimizations and harmonic and anharmonic vibrational frequencies were calculated using the LCCSD(T) method with the cc‐pVTZ basis set. Anharmonic frequencies of fundamental, overtone, and combination transitions were calculated using a variational approach implemented in the P Anhar.v2.0 code, to assign the experimental data for each compound. These results improve our knowledge of these under‐investigated compounds and pave the way for other physicochemical studies on functionalized isocyanides.     

Mesoionic Dithiolates (MIDts) Derived from 1,3-Imidazole-Based Anionic Dicarbenes (ADCs)

Mesoionic dithiolates [(MIDt^Ar)Li(LiBr)₂(THF)₃] (MIDt^Ar={SC(NDipp)}₂CAr; Dipp=2,6-iPr₂C₆H₃; Ar=Ph 3 a , 3-MeC₆H₄ (3-Tol) 3 b , 4-Me₂NC₆H₄ (DMP) 3 c ) and [(MIDt^Ph)Li(THF)₂] ( 4 ) are readily accessible (in≥90 % yields) as crystalline solids on treatments of anionic dicarbenes Li(ADC^Ar) ( 2 a - c ) (ADC^Ar={C(NDipp)₂}₂CAr) with elemental sulfur. 3 a - c and 4 are monoanionic ditopic ligands with both the sulfur atoms formally negatively charged, while the 1,3-imidazole unit bears a formal positive charge. Treatment of 4 with (L)GeCl₂ (L=1,4-dioxane) affords the germylene (MIDt^Ph)GeCl ( 5 ) featuring a three-coordinated Ge atom. 5 reacts with (L)GeCl₂ to give the Ge−Ge catenation product (MIDt^Ph)GeGeCl₃ ( 6 ). KC₈ reduction of 5 yields the homoleptic germylene (MIDt^Ph)₂Ge ( 7 ). Compounds 3 a - c and 4 – 7 have been characterized by spectroscopic studies and single-crystal X-ray diffraction. The electronic structures of 4 – 7 have been analyzed by DFT calculations.     

Well-posedness of the fundamental boundary value problems for constrained anisotropic elastic materials

We consider the equations of linear homogeneous anisotropic elasticity admitting the possibility that the material is internally constrained, and formulate a simple necessary and sufficient condition for the fundamental boundary value problems to be well-posed. For materials fulfilling the condition, we establish continuous dependence of the displacement and stress on the elastic moduli and ellipticity of the elasticity system. As an application we determine the orthotropic materials for which the fundamental problems are well-posed in terms of their Young's moduli, shear moduli, and Poisson ratios. Finally, we derive a reformulation of the elasticity system that is valid for both constrained and unconstrained materials and involves only one scalar unknown in addition to the displacements. For a two-dimensional constrained material a further reduction to a single scalar equation is outlined.This paper is dedicated to Professor Joachim Nitsche on the occasion of his sixtieth birthday     

Anionic Graft Copolymers. ll. Styrene Grafts on EPT Rubbers

Rubbers containing a low level of unsaturation such as EPT may be metalated with a chelate made from s-butyllithium and N,N,N′- N′ -tetramethylethylethylenediamine. The lithiated polymers, reacted with styrene, result in polystyrene graft copolymers. The physical properties are affected by graft level and polystyrene content.     

Anionic Graft Copolymers. III. Hydrogenation of Polydienes Grafted with Vinylaromatics

A new method is described to prepare graft copolymers of polystyrene and polyvinylcyclohexane on polyethylene and poly (ethylene, butene-1). Hydrogenation of the butadiene moieties of graft copolymers of polystyrene on poly-1, 4-butadiene and high vinyl polybutadiene forms graft copolymers of polystyrene on polyethylene and on poly (ethylene, butene-1). Graft copolymers of polyvinylcyclohexane on polyethylene and on poly (ethylene, butene-1) are prepared by completely hydrogenating graft copolymers of polystyrene on poly-1, 4-butadiene and on high vinyl polybutadiene. The physical properties of these polymer systems depend on composition and graft level, resulting in either tough polymers or elastomers.     

Testing for a $$\delta $$ -neighborhood of a generalized Pareto copula

Annals of the Institute of Statistical Mathematics - A multivariate distribution function F is in the max-domain of attraction of an extreme value distribution if and only if this is true for the...     

NIEDERKOORDINIERTE PHOSPHORVERBINDUNGEN, 631. IMINO(BISMETHYLEN)PHOSPHATE

Abstract

Two imino(bismethylene)phosphat-ions can be synthesized via reaction of phenylamino- and α-naphthylaminobismethylenephosphorane with n-butyllithium in tetrahydrofuran. Anions containing [sgrave]³λ⁶-bounded phosphorus are stabilized in the crystal with THF-solvated lithium-kations.

Zwei Imino(bismethylen)phosphat-ionen werden durch Umsetzung des Phenylamino- und des α-Naphthylaminobismethylenphosphorans mit n-Butyllithium in Tetrahydrofuran erhalten. Die Anionen mit [sgrave]³λ⁶-gebundenem Phosphor werden im Kristall durch THF-solvatisierte Lithium-Kationen stabilisiert.     

DYNAMIC STEREOCHEMISTRY OF SYMMETRICALLY BUT DIFFERENTLY SUBSTITUTED DIPHOSPHANES

Abstract

The main interest of our work in Bonn during the last years was in the field of phosphorus-carbon compounds with multiple bonds. Beside the synthesis of new classes of compounds we were particularly interested in the amazing analogy between the PC- and the CC-double bond, which could be proved by evidence of E/Z isomers and a clear indication of pericyclic reactions.