Photomechanical Actuation of Ligand Geometry in Enantioselective Catalysis

A catalyst that couples a photoswitch to the biaryl backbone of a chiral bis(phosphine) ligand, thus allowing photochemical manipulation of ligand geometry without perturbing the electronic structure is reported. The changes in catalyst activity and selectivity upon switching can be attributed to intramolecular mechanical forces, thus laying the foundation for a new class of catalysts whose selectivity can be varied smoothly and in situ over a useful range by controlling molecular stress experienced by the catalyst during turnover. Forces on the order of 100 pN are generated, thus leading to measurable changes in the enantioselectivities of asymmetric Heck arylations and Trost allylic alkylations. The differential coupling between applied force and competing stereochemical pathways is quantified and found to be more efficient for the Heck arylations.     

Mechanochemical Formation,Solution Rearrangements,and Catalytic Behavior of a Polymorphic Ca/K Allyl Complex

Without solvents present, the often far-from-equilibrium environment in a mechanochemically driven synthesis can generate high-energy, non-stoichiometric products not observed from the same ratio of reagents used in solution. Ball milling 2 equiv. K[A’] (A’=[1,3-(SiMe₃)₂C₃H₃]⁻) with CaI₂ yields a non-stoichiometric calciate, K[CaA’₃], which initially forms a structure ( 1 ) likely containing a mixture of pi- and sigma-bound allyl ligands. Dissolved in arenes, the compound rearranges over the course of several days to a structure ( 2 ) with only η³-bound allyl ligands, and that can be crystallized as a coordination polymer. If dissolved in alkanes, however, the rearrangement of 1 to 2 occurs within minutes. The structures of 1 and 2 have been modeled with DFT calculations, and 2 initiates the anionic polymerization of methyl methacrylate and isoprene; for the latter, under the mildest conditions yet reported for a heavy Group 2 species (one-atm pressure and room temperature).     

Simulation of laser-driven,ablated plasma flows in collisionless shock experiments on OMEGA and the NIF

Experiments investigating the physics of interpenetrating, collisionless, ablated plasma flows have become an important area of research in the high-energy-density field. In order to evaluate the feasibility of designing experiments that will generate a collisionless shock mediated by the Weibel instability on the National Ignition Facility (NIF) laser, computer simulations using the Center for Radiative Shock Hydrodynamics (CRASH) radiation-hydrodynamics model have been carried out. This paper reports assessment of whether the experiment can reach the required scale size while maintaining the low interflow collisionality necessary for the collisionless shock to form. Comparison of simulation results with data from Omega experiments shows the ability of the CRASH code to model these ablated systems. The combined results indicate that experiments on the NIF are capable of reaching the regimes necessary for the formation of a collisionless shock in a laboratory experiment.