The electronic structure of benzvalene : Photoelectronspectroscopic studies

The photoelectron(PE)spectrum of tricyclo[3.1.0.0^2,6] hex-2-ene(benzvalene 1) has been recorded. The first four bands in the PE spectrum of 1 can be assigned to transitions to ²B₂, ²A₁, ²A₂ and ²B₁ states of 1¹. This assignment is discussed in terms of the results of semiempirical and ab initio calculations on 1. Furthermore the highest occupied MO's of 1 are derived qualitatively from an interaction diagram between a distorted bicyclobutane and an ethylene moiety.     

Der Stoffwechsel von Verbindungen mit Dreifachbindung. VI. Stoffwechselverhalten von Alkincarbonsäuren und Alkindicarbonsäuren

Metabolism of Acetylenic Monocarboxylic and Dicarboxylic Acids Feeding of acetylenic monoacids with chain length of 11 to 18 C-atoms to rats led to excretion of dicarboxylic acids with retained triple bonds. 10-Octadecynoic acid led to the formation of metabolites with even and odd number of C-atoms, suggesting in addition to established ω- and β-oxidation an α-oxidative pathway.     

Pseudohalogenverbindungen. XX. Perfluorierte alkan- und phenylsulfonylpseudohalogenide

The pseudohalide CF₃SO₂NCO has been synthesized by means of a new reaction involving trifluoromethanesulphonamide and chlorosulphonylisocyanate. This method may be used for preparing other perfluorinated alkanesulphonyl-, arenesulphonyl- and alkanecarbonyl-amides. Reactions of CF₃SO₂NCO with alcohols, thiols, phenols and amines lead to the corresponding carbonic acid esters, thio-esters, phenyl esters and ureas. Reactions with carbonic acids, aldehydes and dimethylsulphoxide gave CO₂ and the corresponding acid amides, azomethines and imino-dimethylsulphurane. Under pressure at 160°C, CF₃SO₂NCO reacts with phosphorus pentasulphide to give the previously unknown compound CF₃SO₂NCS; with phosphorus pentachloride under the same conditions, CF₃SO₂NCCl₂ is formed.     

Systematische untersuchungen über das verhalten von organozinnverbindungen gegenüber flüssigem schwefeldioxid II. Reaktionen von arylstannanen mit flüssigem SO2

The behaviour of tetraarylstannanes, R₄Sn (R = C₆H₅CH₂, C₆H₅, o-, m-, p-CH₃C₆H₄), towards SO₂ under various conditions has now been studied in detail. Compared to aliphatic tetraorganostannanes, the variability of the reaction products is much less, so that in nearly all cases only disulfinates, R₂Sn(O₂SR)₂, are formed. The aromatic tin(IV) mono-, di- and tri-sulfinates are also obtained by metathetical reaction between the corresponding organotin halides and sodium sulfinates. A unique feature of triaryltin chlorides, R₃SnCl (R = C₆H₅, o-, m-, p-CH₃C₆H₄), is their disproportionation in liquid SO₂ leading to disulfinates, R₂Sn(O₂SR)₂, and dichlorides, R₂SnCl₂. (p-CH₃C₆H₄)₂SnCl₂, under more efficient conditions, also accepts SO₂ forming (p-CH₃C₆H₄SO₂)₂SnCl₂. The structural investigations of the newly prepared compounds are carried out on the basis of their IR and ¹H NMR spectra.     

2,4-Dimethoxycarbonyl-1,1,3,3-tetrakis(dimethylamino)-1λ5,3λ5-diphosphete

1,1,3,3 - Tetrakis(dimethylamino) - 1λ⁵,3λ⁵ - diphosphete, 1 , reacts with cyanoformic acid methyl ester to form two isomers of the title compound 2 . Properties, NMR, mass, and IR spectra of 2 , as well as the molecular and crystal structure of the E isomer of 2 , are described and discussed.     

Synthesis and characterization of water-soluble palladium(II)-functionalized diphosphine complexes

Water-soluble functionalized bis(phosphine) ligands L (a–h) of the general formula CH₂(CH₂PR₂)₂, where for a: R = (CH₂)₆OH; b–g: R = (CH₂)_nP(O)(OEt)₂, n = 2–6 and n = 8; h: R = (CH₂)₃NH₂ ( Scheme 1), have been prepared photochemically by hydrophosphination of the corresponding 1-alkenes with H₂P(CH₂)₃PH₂. Water-soluble palladium complexes cis-[Pd(L)(OAc)₂] (1–8) were obtained by the reaction of Pd(OAc)₂ with the ligands a–h in a 1:1 mixture of dichloromethane:acetonitrile. The water-soluble phosphine ligands and their palladium complexes were characterized by IR, ¹H and ³¹P NMR. A crystallographic study of complex 1 shows that the Pd(II) ion has a square planar coordination sphere in which the acetate ligands and the diphosphine ligand deviate by less than 0.12 Å from ideal planar.     

Lattice Points in Three-Dimensional Convex Bodies with Points of Gaussian Curvature Zero at the Boundary

 In this article we investigate the number of lattice points in a three-dimensional convex body which contains non-isolated points with Gaussian curvature zero but a finite number of flat points at the boundary. Especially, in case of rational tangential planes in these points we investigate not only the influence of the flat points but also of the other points with Gaussian curvature zero on the estimation of the lattice rest. Received 19 June 2001; in revised form 17 January 2002 RID="a" ID="a" Dedicated to Professor Edmund Hlawka on the occasion of his 85th birthday