Fermi surface studies of non-dilute disordered alloys by positron experiments

The technique of positron annihilation experiments as applied to the study of Fermi surfaces in metals and alloys is briefly reviewed. The angular correlation of the two annihilation photons is directly related to the momentum distribution of the positron-electron system; breaks in this distribution reflect the size and shape of the Fermi surface. Recent two-dimensional angular correlation measurements designed to study the Fermi surface of Cu?Al and Cu?Zn alloys are presented, and are compared with theoretical predictions.     

Beitrag zur Berechnung des Wärmeüberganges und Druckabfalles laminarer Einlaufströmungen

Zusammenfassung In der vorliegenden Arbeit wurden Wärmeübergang und Druckabfall nichtausgebildeter Laminarströmung in Rohren und ebenen Kanälen berechnet. Hierzu wurden exakte Methoden der Grenzschichttheorie, wie sie zur Berechnung der Geschwindigkeitsverteilung üblich sind, auf die Berechnung der Temperaturverteilung übertragen. Diese Methoden bestehen darin, daß man eine Entwicklung von vorn ansetzt, die vom Eintrittsquerschnitt an gültig ist, und eine Entwicklung von hinten, die in größerer Entfernung vom Eintrittsquerschnitt an gilt. In dem Bereich, wo weder die Entwicklung von vorn noch die Entwicklung von hinten gültig sind, weil nicht genügend Glieder zur Verfügung stehen, erzielt man durch Interpolation brauchbare Ergebnisse. Die in der Arbeit beschriebenen Methoden sind auch geeignet, den Wärmeübergang und Druckabfall in Ringspalten zu berechnen. Das wird jedoch eine erhebliche Rechenarbeit erfordern, weil als weiterer Parameter noch das Verhältnis der Radien des inneren und des äußeren Rohres auftritt.Auszug aus der von der Fakultät für Maschinenwesen der Technischen Hochschule Karlsruhe genehmigten Dissertation des Verfassers.     

Zwei neue Oxopalladate: BaPdNd2O5 und BaPdSm2O5 mit planar koordinierten Pd2+-Ionen

Single crystals of BaPdNd₂O₅ (A), BaPdSm₂O₅ (B) and BaCuNd₂O₅ (C) were prepared by solid state reaction using BaCl₂ as a fusing assistant (A, B) or by high temperature Laser technique (C). X-ray investigations show tetragonal symmetry with A:a=6.7387 (5),c=5.9002 (25) Å, B:a=6.6667 (13),c=5.8800 (6) Å (space group D _4h ⁵ ?P4/mbm,Z=2). The formerly investigated compound (C) is refined here by single crystal data. (A) and (B) belong to the BaPtNd₂O₅-type. The results are discussed.     

Olefins as steering ligands for homogeneously catalyzed hydrogenations

Iridium(I) complexes containing a (5H-dibenzo[a,d]cyclohepten-5-yl)-phosphane (tropp(R); R = phosphorus-bound substituent = Ph, Cyc) as a rigid, concave-shaped, mixed phosphane olefin ligand were prepared and tested as catalyst precursors in the hydrogenation of imines. With the complex [Ir(tropp(Cyc))(cod)]OTf, turnover frequencies (TOFs) of >6000 h(-1) were reached in the hydrogenation of N-phenyl-benzylidenamine, PhN==CHPh. Lower activities (TOF>80 h(-1)) are observed with N-phenyl-(1-phenylethylidene)amine, PhN==CMePh. Chiral tropp-type ligands were prepared in few simple steps. Monosubstitution of the olefinic unit in the dibenzo[a,d]cycloheptenyl moiety with (R)- or (S)-mentholate gave mixtures of diastereomers that could be separated and isolated in enantiomerically pure form. Iridium(I) complexes with these ligands are rare examples of side-on bonded enolether complexes. In catalytic imine hydrogenations, complete conversion (>98 %) was reached in all cases (conditions: p[H(2)] = 50 bar, T = 50 degrees C, t = 2 h, substrate/catalyst 100:1). The best enantiomeric excess (ee = 86 % S isomer) was reached with PhN==CMePh as substrate and the R,R form of the (10-menthyloxy-5H-dibenzo[a,d]cyclohepten-5-yl)diphenylphosphane ligand. The iridium(I) complex containing the same phosphane gave a 60 % ee (S isomer) with the enamide N-(1-phenylvinyl)acetamide as substrate (conditions: p[H(2)] = 4 bar, T = 50 degrees C, t = 18 h, substrate/catalyst = 50:1). These reactions constitute the first examples in which chiral olefins have been used as steering ligands in catalytic enantioselective hydrogenations.     

Six- and eightfold palladium-catalyzed cross-coupling reactions of hexa- and octabromoarenes

Palladium-catalyzed sixfold coupling of hexabromobenzene (20) with a variety of alkenylboronates and alkenylstannanes provided hexaalkenylbenzenes 1 in up to 73 % and 16 to 41 % yields, respectively. In some cases pentaalkenylbenzenes 21 were isolated as the main products (up to 75 %). Some functionally substituted hexaalkenylbenzene derivatives containing oxygen or sulfur atoms in each of their six arms have also been prepared (16 to 24 % yield). The sixfold coupling of the less sterically encumbered 2,3,6,7,10,11-hexabromotriphenylene (24) gave the desired hexakis(3,3-dimethyl-1-butenyl)triphenylene (25) in 93 % yield. The first successful cross-coupling reaction of octabromonaphthalene (26) gave octakis-(3,3-dimethyl-1-butenyl)naphthalene (27) in 21 % yield. Crystal structure analyses disclose that, depending on the nature of the substituents, the six arms are positioned either all on the same side of the central benzene ring as in 1 a and 1 i, making them nicely cup-shaped molecules, or alternatingly above and below the central plane as in 1 h and 23. In 27, the four arms at C-1,4,6,7 are down, while the others are up, or vice versa. Upon catalytic hydrogenation, 1 a yielded 89 % of hexakis(tert-butylethyl)benzene (23). Some efficient accesses to alkynes with sterically demanding substituents are also described. Elimination of phosphoric acid from the enol phosphate derived from the corresponding methyl ketones gave 1-ethynyladamantane (3 b, 62 % yield), 1-ethynyl-1-methylcyclohexane (3 c, 85 %) and 3,3-dimethylpentyne (3 e, 65 %). 1-(Trimethylsilyl)ethynylcyclopropane (7) was used to prepare 1-ethynyl-1-methylcyclopropane (3 d) (two steps, 64 % overall yield). The functionally substituted alkynes 3 f-h were synthesized in multistep sequences starting from the propargyl chloride 11, which was prepared in high yields from the dimethylpropargyl alcohol 10 (94 %). The alkenylstannanes 19 were prepared by hydrostannation of the corresponding alkynes in moderate to high yields (42-97 %), and the alkenylboronates 2 and 4 by hydroboration with catecholborane (27-96 % yield) or pinacolborane (26-69 % yield).     

How plants keep dry: a physicist's point of view

This work describes the investigation of the physical basis of the amazing water repellence of some plant leaves, which is in addition to self-cleaning properties known as the "Lotus effect". Two rather different possible mechanisms are proposed, which are suggested to cover the main physics in a majority of superhydrophobic systems. These concepts are illustrated with two different types of plant leaves as well as a model surface carrying carbon nanotube aggregates.     

On Cyclic Packing of a Tree

We prove that there exists a packing of copies of a tree of size into K_n. Moreover, the proof provides an easy algorithm.Acknowledgments. The research of the second author was partially supported by Deutscher Akademischer Austauschdienst.