Structural studies on ruthenium(II) complexes used in interphase catalysis for the hydrogenation of ketones

Structural studies were performed on catalytically active ruthenium(II) complexes used in interphases, by means of XAFS spectroscopy. The EXAFS investigations indicate that the complexes retain their structural integrity when they are embedded on polysiloxane matrices to form stationary phase materials. The AXAFS studies reveal that the variations in the catalytic activity of the complexes with different ligands can be correlated to the differences in the electronic structure around the active ruthenium center. The EXAFS investigations show that, in asymmetric transfer hydrogenation reactions catalysed by ruthenium(II) complexes, the co‐catalyst plays a crucial role not only in enhancing the catalytic activity, but also in determining the structure of the intermediate species. Copyright © 2007 John Wiley & Sons, Ltd.     

On the Asymptotics of Fekete-Type Points for Univariate Radial Basis Interpolation

Suppose that K ^d is compact and that we are given a function fC(K) together with distinct points x_iK, 1in. Radial basis interpolation consists of choosing a fixed (basis) function g : ⁺→ and looking for a linear combination of the translates g(|x−x_j|) which interpolates f at the given points. Specifically, we look for coefficients c_j such that has the property that F(x_i)=f(x_i), 1in. The Fekete-type points of this process are those for which the associated interpolation matrix [g(|x_i−x_j|)]_1i,jn has determinant as large as possible (in absolute value). In this work, we show that, in the univariate case, for a broad class of functions g, among all point sequences which are (strongly) asymptotically distributed according to a weight function, the equally spaced points give the asymptotically largest determinant. This gives strong evidence that the Fekete points themselves are indeed asymptotically equally spaced.     

On the differentiability of maps into Lie transformation groups

Let G be a Lie transformation group on a manifold M. Then a map f: NG is differentiable, iff for every point pM the map q f(q)·p is differentiable.     

On static and radiative space-times

The conformal constraint equations on space-like hypersurfaces are discussed near points which represent either time-like or spatial infinity for an asymptotically flat solution of Einstein's vacuum field equations. In the case of time-like infinity a certain radiativity condition, is derived which must be satisfied by the data at that point. The case of space-like infinity is analysed in detail for static space-times with non-vanishing mass. It is shown that the conformal structure implied here on a slice of constant Killing time, which extends analytically through infinity, satisfies at spatial infinity the radiativity condition. Thus to any static solution exists a certain radiative solution which has a smooth structure at past null infinity and is regular at past time-like infinity. A characterization of these solutions by their free data is given and non-symmetry properties are discussed.     

Strukturelle Charakterisierung der Dicyanamid-Komplexe von Kupfer(II), Nickel(II) bzw. Kobalt(II) mit Aminopyridinen

Summary New dicyanamide complexes of the typeM[N(CN)₂]₂ L ₂ (M=Cu or Ni;L=2-, 3-, 4-aminopyridine, 2-amino-5-nitropyridine) and Co[N(CN)₂]₂ (2-amino-5-nitropyridine)₂ were prepared and studied by spectroscopic methods as well as by room-temperature magnetic moments. The results show that the Cu(II) complexes have elongated pseudooctahedral structures while the Ni(II) and Co(II) complexes are octahedral. In most cases the N(CN)₂ groups are in bridging function and through their cyanide nitrogens, or-more rarely-amide and cyanide nitrogens connect the basic structure units into polymeric conglomerates. In the Cu(II) systems exchange coupling is seen from the _eff value or ESR spectrum.

Professor Viktor Gutmann zum 70. Geburtstag gewidmet     

Adducts of Rh2[MTPA]4 with some phosphine chalcogenides: nature of binding and ligand exchange

Adducts of four phosphine chalcogenides with the chiral dirhodium complex ([Rh-Rh]) were investigated by variable-temperature 1H and 31P NMR spectroscopy in order to compare their properties as axial ligands. Whereas the selenide (1) and the sulfide (2) are strong ligands with electrostatic attraction and, in addition, a significant orbital (HOMO-LUMO) interaction, the phosphine oxide compounds (P=O) bind primarily via electrostatic attraction and are relatively weak donors. Moreover, the overall bond strength in these adducts depends on steric congestion around the P=O group.