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).     

Mesoionic bora-tetraazapentalenes--fully reversible two step redox systems

Bora-tetraazapentalenes have been synthesised and characterized; the radical anion shows an unusual thermodynamic stability (semiquinone formation constants K(SEM) of ca. 10(14)).     

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.     

Exact Solution of the AVZ-Hamiltonian in the Grand-Canonical Ensemble

The thermodynamic behavior of the Angelescu-Verbeure-Zagrebnov (AVZ) Hamiltonian [1], also called the superstable Bogoliubov model, is solved for any temperature and any chemical potential. It is found that its thermodynamics coincides with one for the Mean-Field Gas for small chemical potential or high temperature. However, for large chemical potential or low temperature, a non-conventional Bose condensation appears with, even at zero-temperature, a (non-zero) particle density outside the condensate. Following [2], the analysis in the present paper corresponds to the main technical step to deduce, in the canonical ensemble, a new microscopic theory of superfluidity at all temperatures explained in [3]. Communicated by Vincent Pasquier Submitted 31/03/03, accepted 01/12/03