Reactivity of a N-Coordinated Germylene-Borane Complex: From Ge→B to Ge→Ga Coordination

Reactivity studies of the Ge^II→B complex L(Cl)Ge⋅BH₃ ( 1 ; L=2-Et₂NCH₂-4,6-tBu₂-C₆H₂) were performed to determine the effect on the Ge^II→B donation. N-coordinated compounds L(OtBu)Ge⋅BH₃ ( 2 ) and [LGe⋅BH₃]₂ ( 3 ) were prepared. The possible tuning of the Ge^II→B interaction was proved experimentally, yielding compounds 1-PPh₂-8-(LGe)-C₁₀H₆ ( 4 ) and L(Cl)Ge⋅GaCl₃ ( 5 ) without a Ge^II→B interaction. In 5 , an unprecedented Ge^II→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the Ge^II→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.     

The HITRAP project at GSI: trapping and cooling of highly-charged ions in a Penning trap

A decelerator will be installed at GSI in order to provide and study heavy nuclei without or with only few electrons at very low energies or even at rest. Highly-charged ions will be produced by stripping at relativistic energies. After electron cooling and deceleration in the Experimental Storage Ring (ESR) the ions are ejected out of the storage ring at 4 MeV/u and further decelerated in a combination of linear accelerator structures operated in reverse. Finally, they are injected into a Penning trap where the ions are cooled to 4 K by electron cooling in combination with resistive cooling. From here, the ions can be transferred in a quasi DC or in a pulsed mode to different experimental setups. This article describes the technical concepts of this project focused on the Penning trap.      

Ab initio path-integral molecular dynamics

A path-integral molecular dynamics technique for strongly interacting atoms using ab initio potentials derived from density functional theory is implemented. This allows the efficient inclusion of nuclear quantum dispersion in ab initio simulations at finite temperatures. We present an application to the quantum cluster H ₅ ⁺ .     

Interpolatory integration rules and orthogonal polynomials with varying weights

We investigate which types of asymptotic distributions can be generated by the knots of convergent sequences of interpolatory integration rules. It will turn out that the class of all possible distributions can be described exactly, and it will be shown that the zeros of polynomials that are orthogonal with respect to varying weight functions are good candidates for knots of integration rules with a prescribed asymptotic distribution.Research supported by the Deutsche Forschungsgemeinschaft (AZ: Sta 299/4-2).     

On the convergence of generalized Padé approximants

Letf be an analytic function with all its singularities in a compact set \(E_f \subset \bar C\) of (logarithmic) capacity zero. The function may have branch points. The convergence of generalized (multipoint) Padé approximants to this type of function is investigated. For appropriately selected schemes of interpolation points, it is shown that close-to-diagonal sequences of generalized Padé approximants converge in capacity tof in a certain domain that can be characterized by the property of the minimal condenser capacity. Using a pole elimination procedure, another set of rational approximants tof is derived from the considered generalized Padé approximants. These new approximants converge uniformly on a given continuum \(V \subset \bar C\backslash E_f\) with a rate of convergence that has been conjectured to be best possible. The continuumV is assumed not to divide the complex plane.     

Mechanistic study of alcohol oxidation by the Pd(OAc)(2)/O(2)/DMSO catalyst system and implications for the development of improved aerobic oxidation catalysts

The Pd(OAc)2/O2/DMSO catalyst system displays impressive versatility in the aerobic oxidation of organic substrates, ranging from alcohols to olefins. This report details mechanistic insights into these reactions. Dimethyl sulfoxide (DMSO) plays no redox role in the chemistry, and kinetic experiments identify the turnover-limiting step as DMSO-promoted oxidation of palladium(0) by molecular oxygen. The "chemical oxidase" pathway characterized for this catalyst system holds great promise for the design of new aerobic oxidation reactions.     

The mechanism of the loss of H2 and H2O from 1,4-cyclohexanediol anion and related compounds

Losses of H₂ and H₂O from the [M-H]^? alkoxide anions of 1,4-cyclohexanediol formed in OH^? negative chemical ionization were studied using synthetic deuterated analogues and labelling by hydrogen-deuterium exchange between neutrals in the ion source prior to ionization. Simple 1,2-H₂ elimination leading to an enolate ion does not occur, but stereospecific mechanisms are shown to give a ketolate intermediate daughter ion. Collisionally activated dissociation spectra of the resulting daughter ions are the same as those of the corresponding ions generated directly from ketols.     

Copolymerization parameters of methyl methacrylate and acrylic acid

The relative reactivity of acrylic acid is known to be influenced by the polymerization medium. Nonetheless, the more commonly used reactivity ratios do not show this dependence because they were calculated from low-conversion polymerizations. We have studied the copolymerization of acrylic acid and methyl methacrylate in a number of non-hydrogen-bonding and hydrogen-bonding solvents. We found that the acrylic acid fraction in the copolymer was larger when copolymerized in a non-hydrogen-bonding medium and that the methyl methacrylate fraction was larger when copolymerized in a hydrogen-bonding medium. The precise reactivity ratios were reported when toluene, benzene, isopentyl, acetate, ethyl acetate, methyl formate, and tert-butyl alcohol were used as the polymerization medium. The values were obtained by chromatographic analysis of residual monomer, followed by computation based on the nonlinear, least-squares technique of Tidwell and Mortimer.