Z-Selective Homodimerization of Terminal Olefins with a Ruthenium Metathesis Catalyst

The cross-metathesis of terminal olefins using a novel ruthenium catalyst results in excellent selectivity for the Z-olefin homodimer. The reaction was found to tolerate a large number of functional groups, solvents, and temperatures while maintaining excellent Z-selectivity, even at high reaction conversions

Z-Selectivity in Olefin Metathesis with Chelated Ru Catalysts: Computational Studies of Mechanism and Selectivity

The mechanism and origins of Z-selectivity in olefin metathesis with chelated Ru catalysts were explored using density functional theory. The olefin approaches from the “side” position of the chelated Ru catalysts, in contrast to reactions with previous unchelated Ru catalysts that favor the bottom-bound pathway. Steric repulsions between the substituents on the olefin and the N-substituent on the N-heterocyclic carbene ligand lead to highly selective formation of the Z product

On the motion of hairy black holes in Einstein-Maxwell-dilaton theories

Starting from the static, spherically symmetric black hole solutions in massless Einstein-Maxwell-dilaton (EMD) theories, we build a "skeleton" action, that is, we phenomenologically replace black holes by an appropriate effective point particle action, which is well suited to the formal treatment of the many-body problem in EMD theories. We find that, depending crucially on the value of their scalar cosmological environment, black holes can undergo steep "scalarization" transitions, inducing large deviations to the general relativistic two-body dynamics, as shown, for example, when computing the first post-Keplerian Lagrangian of EMD theories

Stereoselective Access to Z and E Macrocycles by Ruthenium-Catalyzed Z-Selective Ring-Closing Metathesis and Ethenolysis

The first report of Z-selective macrocyclizations using a ruthenium-based metathesis catalyst is described. The selectivity for Z macrocycles is consistently high for a diverse set of substrates with a variety of functional groups and ring sizes. The same catalyst was also employed for the Z-selective ethenolysis of a mixture of E and Z macrocycles, providing the pure E isomer. Notably, an ethylene pressure of only 1 atm was required. These methodologies were successfully applied to the construction of several olfactory macrocycles as well as the formal total synthesis of the cytotoxic alkaloid motuporamine C

Z-Selective Ethenolysis with a Ruthenium Metathesis Catalyst: Experiment and Theory

The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups

Improved Ruthenium Catalysts for Z-Selective Olefin Metathesis

Several new C–H-activated ruthenium catalysts for Z-selective olefin metathesis have been synthesized. Both the carboxylate ligand and the aryl group of the N-heterocyclic carbene have been altered and the resulting catalysts evaluated using a range of metathesis reactions. Substitution of bidentate with monodentate X-type ligands led to a severe attenuation of metathesis activity and selectivity, while minor differences were observed between bidentate ligands within the same family (e.g., carboxylates). The use of nitrato-type ligands in place of carboxylates afforded a significant improvement in metathesis activity and selectivity. With these catalysts, turnover numbers approaching 1000 were possible for a variety of cross-metathesis reactions, including the synthesis of industrially relevant products

On the Equation of State of Nuclear Matter in 158A GeV Pb+Pb Collisions

Within a hydrodynamical approach we investigate the sensitivity of single inclusive momentum spectra of hadrons in 158A GeV Pb+Pb collisions to three different equations of state of nuclear matter. Two of the equations of state are based on lattice QCD results and include a phase transition to a quark-gluon plasma. The third equation of state has been extracted from the microscopic transport code RQMD under the assumption of complete local thermalization. All three equations of state provide reasonable fits to data taken by the NA44 and NA49 Collaborations. The initial conditions before the evolution of the fireballs and the space-time evolution pictures differ dramatically for the three equations of state when the same freeze-out temperature is used in all calculations. However, the softest of the equations of state results in transverse mass spectra that are too steep in the central rapidity region. We conclude that the transverse particle momenta are determined by the effective softness of the equation of state during the fireball expansion.Comment: 4 pages, including 4 figures and 2 tables. For a PostScript file of the manuscript, you can also goto http://t2.lanl.gov/schlei/eprint.htm

Decomposition Pathways of Z-Selective Ruthenium Metathesis Catalysts

The decomposition of a Z-selective ruthenium metathesis catalyst and structurally similar analogues has been investigated utilizing X-ray crystallography and density functional theory. Isolated X-ray crystal structures suggest that recently reported C–H activated catalysts undergo decomposition via insertion of the alkylidene moiety into the chelating ruthenium–carbon bond followed by hydride elimination, which is supported by theoretical calculations. The resulting ruthenium hydride intermediates have been implicated in previously observed olefin migration, and thus lead to unwanted byproducts in cross metathesis reactions. Preventing these decomposition modes will be essential in the design of more active and selective Z-selective catalysts

Thermal photons as a measure for the rapidity dependence of the temperature

The rapidity distribution of thermal photons produced in Pb+Pb collisions at CERN-SPS energies is calculated within scaling and three-fluid hydrodynamics. It is shown that these scenarios lead to very different rapidity spectra. A measurement of the rapidity dependence of photon radiation can give cleaner insight into the reaction dynamics than pion spectra, especially into the rapidity dependence of the temperature.Comment: 3 Figure