Metallorganische Verbindungen mit N-substituierten 3-Hydroxy-2-methyl-4-pyridon-Liganden: quadratisch-planare Rhodium(I)-, Iridium(I)- und Palladium(II)-Komplexe

Organometallic Compounds with N -substituted 3-Hydroxy-2-methyl-4-pyridone Ligands: square planar Rhodium(I), Iridium(I), and Palladium(II) Complexes Reactions of [(OC)₂MCl]₂ (M = Rh, Ir) or [(cod)RhCl]₂ with the anions of N-Aryl or N-Alkyl substituted 3-hydroxy-2-methyl-4-pyridones (O–O′) yield complexes of the general formula [L₂M(O–O′)]. Compounds of this type are also available from reactions of [(OC)₂Rh(acac)] with the corresponding neutral ligands. Substitution of one carbonyl-ligand of the N-phenyl complex [(OC)₂Rh(C₁₂H₁₀NO₂)] ( 2 ) with cyclooctene affords [(OC)(C₈H₁₄)Rh(C₁₂H₁₀NO₂)] ( 8 ). The palladium complexes [(R₃P)Pd(O–O′)Cl] (R = Et, Bu), [(C₆H₄CH₂NMe₂) · Pd(O–O′)] and [(Et₃P)₂Pd(O–O′)]BF₄ ( 9 – 12 ) were synthesized from [(R₃P)PdCl₂]₂, [(C₆H₄CH₂NMe₂)PdCl]₂ or [(Et₃P)PdCl₂]. The structures of the N-methyl compounds [(OC)₂Rh(C₇H₈NO₂)] ( 1 ) and [(Ph₃P)Pd(C₇H₈NO₂)Cl] ( 9 ) were determined by single crystal X-ray diffraction.     

Aggregate, Polymer and Cluster Formation from Metal-Imino Carboxylate Complexes

Reaction of tris-(2-aminoethyl)amine (tren) andthe sodium salt of an -ketocarboxylic acid, typically sodium pyruvate, affordsin the presence of a lanthanide ion aseries of complexes and aggregates includingmononuclear, cyclic tetranuclear and polymerspecies of [L¹]^3- ([L¹]^3-=N[CH₂CH₂N=C(CH₃)COO^-]³).The aggregation of these and related d-block elementcomplexes with Na⁺ ions leadsto the formation of polymeric materials, and thefactors influencing the formation and controlof these various aggregation states are discussed.Metal cations also template the aggregationof the fragment [Ni(L²)] ([L²]^2- =CH₂[CH₂N = C(CH₃)COO^-]₂)to give, in high yield, the polynuclearaggregates {[Ni(L²)]₆M}^x+(M = Nd, Pr, Ce, La, x = 3; M = Sr, Ba, x = 2). The structures of{[Ni(L²)]₆M}^x+ show aninterstitial twelve co-ordinate, icosahedralcation M^x+ encapsulated by six [Ni(L²)]fragments. In the presence ofNa⁺, aggregation of [Ni(L²)] fragments affords {[Ni(L²)]₉Na₄(H₂O)(MeOH)(ClO₄)}³⁺ thestructure of whichshows four Na⁺ ions templating the formation ofa distorted tricapped trigonal prismatic[Ni(L²)]₉ cage. Thus, control overconstruction of various polynuclear cages viaself-assembly at octahedral junctions can beachieved using main group, transition metaland lanthanide ion templates.     

Backbone rearrangements of methyl (-)-kaur-9(11)-en-19-oate and its epoxide: structures of two diterpenes of a new skeletal type

cleavage of the epoxide ($\text{2}$) of methyl (-)-kaur-9(11)-en-19-oate ($\text{1b}$) with boron trifluoride-ether in benzene and in acetic anhydride yielded ($\text{3a}$) and ($\text{3b}$), respectively. On epoxidation with $\text{m}$-chloroperbenzoic acid in the presence of $\text{N}$-nitrosomethyl urea, ($\text{1b}$) suffered a backbone rearrangement to form ($\text{6}$).     

Interaction-induced collapse of a section of the Fermi sea in the zigzag Hubbard ladder

Using the next-nearest-neighbor (zigzag) Hubbard chain as a one-dimensional model, we investigate the influence of interactions on the position of the Fermi wave vectors with the density-matrix renormalization-group technique. For suitable choices of the hopping parameters we observe that electron-electron correlations induce very different renormalizations for the two different Fermi wave vectors, which ultimately lead to a complete destruction of one section of the Fermi sea in a quantum critical point.     

A beaker without walls: formation of deeply supercooled binary liquid solutions of alcohols from nanoscale amorphous solid films

Layered nanoscale amorphous solid films of methanol and ethanol undergo complete intermixing prior to the onset of measurable desorption at 120 K. This intermixing precedes and inhibits crystallization. Subsequent desorption of the film is described quantitatively by a kinetic model describing evaporation from a continuously mixed ideal binary liquid solution. This occurs at temperatures below the melting point of the binary mixture, indicating ideal behavior for the supercooled liquid solution. This approach provides a new method for preparing and examining deeply supercooled solutions.     

The echocardiophone: A new means for observing spatial movement of the heart

The paper describes a new pocket size instrument called the ‘Cardiophone’ for the diagnosis of cardiac dysfunction. It is a continuous wave swept frequency ultrasonic echo-location system which produces dynamic auditory signals corresponding to the positional change of internal structures of the heart. The four valves are relatively easy to locate compared with conventional ECG machines. Preliminary clinical evaluation results are presented indicating the potential of the instrument for the general practitioner.     

Vapor-liquid equilibria in binary mixtures formed from hexamethyldisiloxane,toluene and ethanol

Vapor-liquid equilibria have been measured in the binary systems hexamethyldisiloxane-toluene, hexamethyldisiloxane-ethanol and toluene-ethanol between 333.15 and 358.15 K and the results have been correlated using the Wilson equation. All three binary systems exhibit azeotropic behavior in the temperature range studied.     

In-out semi-classical gravity and 1N quantum gravity

Classical gravity with higher derivatives, when coupled to the in-out matrix element of T_μν: (a) appears to be free from instabilities of the in-in theory; (b) may be considered as the “underlying classical theory” to Tomboulis' $\text{1}\text{N}\text{-}\text{resummed}$ quantum gravity. I explain how these two facts may be adduced as evidence for the viability both of the former semi-classical approximation and of the latter approach to full quantum gravity.     

Shock-wave velocity of a femtosecond-laser-produced plasma

Fluorescence measurements have been used to characterize the velocity of atoms in a femtosecond-laser-produced plasma. Nanogram amounts of a copper sample were ablated by the focused radiation (λ=775 nm) of an all-solid-state laser. The laser was operated at a pulse rate of 10 Hz with an energy of 200μJ per pulse. The microplasma expanded into a defined argon atmosphere of pressures between 0.02 and 850 mbar. Atomic fluorescence was excited in the laser plume by a dye-laser pulse with the wavelength set to the line Cu I 282.4 nm. The narrowed beam of the dye-laser was directed into the plasma at different heights above the sample surface. The fluorescence radiation was measured with an échelle-spectrometer, equipped with an intensified-charge-coupled device as the detector. The velocity depends strongly on the pressure of the ambient atmosphere and the distance from the sample surface. The highest velocity found at an argon pressure of 0.02 mbar was 1.0×10⁶ cm s⁻¹.