Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes

A first example of an Et₂Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.     

Families of Line-Graphs and Their Quantization

Any directed graph G with N vertices and J edges has an associated line-graph L(G) where the J edges form the vertices of L(G). We show that the non-zero eigenvalues of the adjacency matrices are the same for all graphs of such a family L ⁿ (G). We give necessary and sufficient conditions for a line-graph to be quantisable and demonstrate that the spectra of associated quantum propagators follow the predictions of random matrices under very general conditions. Line-graphs may therefore serve as models to study the semiclassical limit (of large matrix size) of a quantum dynamics on graphs with fixed classical behaviour.     

A Particle-Mesh Method for the Shallow Water Equations Near Geostrophic Balance

In this paper we outline a new particle-mesh method for rapidly rotating shallow water flows based on a set of regularized equations of motion. The time-stepping method uses an operator splitting of the equations into an Eulerian gravity wave part and a Lagrangian advection part. An essential ingredient is the advection of absolute vorticity by means of translated radial basis functions. We show that this implies exact conservation of enstrophy. The method is tested on two model problems based on the qualitative features of the solutions obtained (i.e., dispersion or smoothness of potential vorticity contours) as well as on the increase in mean divergence level.     

Organoselenium chemistry : A study of intermediates in the fragmentation of aliphatic ketoselenoxides. Characterization of selenoxides,selenenamides and selenolseleninates by 1H-,13C-and 77Se-NMR

A series of β-ketoselenenic acids was generated at low temperature ( - 20° to - 50°) by selenoxide syn elimination of appropriate selenoxides (13-ox, 16-ox, 35-ox, 38-ox, and 39-ox). No evidence for the buildup of significant concentrations of selenenic acid was obtained. A selenolseleninate (15, 2,2' - diseleno - bis(1 - phenyl - 2 - methyl -1 - propanone) - Se - oxide) was detected as an intermediate in the decomposition of 13-ox and 16-ox. This compound, which is stable in solution below - 50° was charaeterized by NMR spectroscopy (¹H, ¹³C,⁷⁷Se) and by its thermal decomposition and reactions with phosphite (reduction to diselenide 6) and dialkylamines (formation of selenenamide 11). Decomposition of 15 in the presence of dibenzylamine resulted in trapping of a selenenic acid-like species (RSeSeOH) to give RSeSeN(CH₂Ph)₂ (R = PhC(O)C(CH₃)₂). Although 15 could not be prepared by oxidation of diselenide 6, it was possible to prepare a cyclic selenolseleninate (4,4-dimethyl-1,2-diselenolane monoxide, 20) by oxidation of the related diselenide (19). Attempts to prepare more stable aliphatic selenenic acids by blocking the principal decomposition pathway of 15 were not successful. Thus 1 - benzoyl -1 - cyclopropaneselenenic acid was generated from 35-ox and 38-ox and 1 - benzoyl - 2,2 - dimethylcyclopropaneselenenic from 39-ox. The former underwent normal disproportionation (to 36 and 37) even when prepared at -49°. The latter gave what appeared to be a selenolseleninate (40) which again disproportionated at -17°.     

Synthese und Strukturuntersuchungen von Ba2H[α-FeO4W12O36] · 26 H2O

Synthesis and Structure Studies of Ba₂H[α-FeO₄W₁₂O₃₆] · 26 H₂O The heteropolyanion compound Ba₂H[α-FeO₄W₁₂O₃₆] · 26 H₂O (I) crystallizes in the tetragonal space group P4 n2 with the lattice parameters a = 12.398(6), c = 18.721(6) Å; Z = 2; D_x = 4.128 g · cm^?3. The structure was solved on a twinned crystal from 1029 observed reflections and refined to an index R of 7.6%. The calculations were done by means of a modified ORFLS-programme by Eitel and Bärnighausen. The heteropolyanion [α-FeO₄W₁₂O₃₆]^5? has the well known α-Keggin structure. The average distance of the four central oxygen atoms to the Fe^III position (0, 0, 0) is 1.84 Å. The angles ? O? Fe? O are 112.3° (4X) and 103.9 (2X), respectively, which leads to an disphenoidal distortion of the FeO₄ tetrahedron. The powder and single crystal ESR spectra of I show the anisotropy of the Fe^III fine structure transition 1/2 ? ?1/2. The Mößbauer spectra confirm the tetragonal distortion of the central FeO₄ tetrahedron (quadrupole splitting Δ ≈ 0.50 mm · s^?1).     

Über die thermischen Eigenschaften von Heteropolysäuren des Typs H3+n[PVnMo12−nO40] · x H2O (n = 0, 1, 2, 3) II. Raman- und IR-spektroskopische Untersuchungen

On the Thermal Behaviour of Heteropoly Acids of the Type H_3+n[PV_nMo_12?nO₄₀] · x H₂O (n = 0, 1, 2, 3). II. Raman and Infrared Spectroscopic Investigations The investigation of de- and rehydratization of the heteropoly acids H_3+n[PV_nMo_12?nO₄₀] · x H₂O (n = 0, 1, 2, 3) shows typical changes in the region of valence and bridging vibrations in the Raman and infrared spectra, in particular during the existence of ?anhydrous”? forms. The time dependence of rehydratization is also demonstrated well with a special Raman sample technique.     

Schwingungsspektroskopische Untersuchungen an den Organohydrogensilanen (XCH2)(CH3)2SiH (X = Cl,Br, J), X(YO)2SiH (X = CH3, C2H5/Y = CH3, C2H5 … tert.-C4H9), (C6H5)2SiH2 und C6H5SiH3

Infrared and Raman Spectroscopic Investigations on the Organosubstituted Silicon Hydrides (XCH₂)(CH₃)₂SiH (X = Cl, Br, J), X(YO)₂SiH (X = CH₂, C₂H₅/Y = CH₃, C₂H₅ … tert.-C₄H₉), (C₆H₅)₂SiH₂ and C₆H₅SiH₃ Typical band splittings, specially for the SiH stretching vibration, are shown in the infrared and Raman spectra of the silicon hydrides (XCH₂)(CH₃)₂SiH (X = Cl, Br, J), and X(YO)₂SiH (X = CH₃, C₂H₅/Y = CH₃, C₂H₅ … tert.-C₄H₉). The cause of this behavior is in all probability the existence of rotational isomers. Raman polarization measurements at organosubstituted silicon di- and trihydrides demonstrate the accidental degeneracy of the SiH valence vibrations.