Basic Promotors Impact Thermodynamics and Catalyst Speciation in Homogeneous Carbonyl Hydrogenation.

Homogeneously catalyzed reactions often make use of additives and promotors that affect reactivity patterns and improve catalytic performance. While the role of reaction promotors is often discussed in view of their chemical reactivity, we demonstrate that they can be involved in catalysis indirectly. In particular, we demonstrate that promotors can adjust the thermodynamics of key transformations in homogeneous hydrogenation catalysis and enable reactions that would be unfavorable otherwise. We identified this phenomenon in a set of well-established and new Mn pincer catalysts that suffer from persistent product inhibition in ester hydrogenation. Although alkoxide base additives do not directly participate in inhibitory transformations, they can affect the equilibrium constants of these processes. Experimentally, we confirm that by varying the base promotor concentration one can control catalyst speciation and inflict substantial changes to the standard free energies of the key steps in the catalytic cycle. Despite the fact that the latter are universally assumed to be constant, we demonstrate that reaction thermodynamics and catalyst state are subject to external control. These results suggest that reaction promotors can be viewed as an integral component of the reaction medium, on its own capable of improving the catalytic performance and reshaping the seemingly rigid thermodynamic landscape of the catalytic transformation.

Stabilization of liquid crystal blue phases by carbon nanoparticles of varying dimensionality.

The thermal stabilization of blue phases is a subject that has been of scientific and technological interest since their discovery. Meanwhile, carbonaceous nanomaterials such as C60 fullerenes, carbon nanotubes and graphene have generated interdisciplinary interest spanning across solid-state physics, organic chemistry, colloids, all the way to soft matter physics. Herein, the stabilization of liquid crystal blue phases by doping with C60, single-walled carbon nanotubes and graphene oxide is described. All three types of particles are found to extend the combined temperature range of blue phases I and II by a factor of ∼5. Furthermore, mixtures of pairs of different materials, and all three types are shown to stabilize the blue phases. The temperature range of the blue phases is shown to grow at the expense of the cholesteric phase. This leads to a blue phase-cholesteric-smecticA phase triple-point in all cases except that of doping with carbon nanotubes. The mechanisms of this thermal stabilization are discussed in light of theoretical descriptions for other established systems.