Selective Cross-Metathesis Versus Ring-Closing Metathesis of Terpenes, Taking the Path Less Travelled.

A diiodo ruthenium olefin metathesis pre-catalyst was employed to achieve remarkably selective cross-metathesis reactions of prenylated 1,6-dienes, effectively overcoming the entropically favored intramolecular ring-closing metathesis. This reaction was investigated using Density Functional Theory (DFT) computations and fine-tuned through the application of a Design of Experiments (DoE) approach. The potential of this innovative process was demonstrated through the unprecedented functionalization of various terpene natural products via cross-metathesis, resulting in the synthesis of new derivatives in a single step.

Light-induced MOF synthesis enabling composite photothermal materials.

Metal-organic frameworks (MOFs) are a class of porous materials known for their large surface areas. Thus, over the past few decades the development of MOFs and their applications has been a major topic of interest throughout the scientific community. However, many current conventional syntheses of MOFs are lengthy solvothermal processes carried out at elevated temperatures.

Latency for All: Enabling Latency of Hoveyda-Grubbs Second-Generation Catalysts by Adding Phosphite Ligands.

The Hoveyda-Grubbs catalyst (, M720 Umicore) is among the most widely used catalysts in olefin metathesis reactions. Given the usefulness of and the great interest in developing latent olefin metathesis catalysts for numerous applications, we developed a method to introduce phosphite molecules as ancillary ligands into the precatalyst framework. This modification alters the geometry of the complex from an active -dichloro form to a latent -dichloro species.

Photothermally heated colloidal synthesis of nanoparticles driven by silica-encapsulated plasmonic heat sources.

Using photons to drive chemical reactions has become an increasingly important field of chemistry. Plasmonic materials can provide a means to introduce the energy necessary for nucleation and growth of nanoparticles by efficiently converting visible and infrared light to heat. Moreover, the formation of crystalline nanoparticles has yet to be included in the extensive list of plasmonic photothermal processes.

Right Answer for the Right Reason? Benchmarking Protocols and Pitfalls on a Ru-Metathesis Example.

A layered meta-benchmarking analysis was devised with the aim of illustrating how to produce an experimental/computational protocol for the method selection and estimation of Gibbs energies of catalytically prominent reactions. Our test subject involved the active-latent equilibrium through the cis-trans isomerism of two metathesis catalysts: mesitylene-Ru-SCF-Cl and diisopropylphenyl-Ru-SCF-Cl. The strategy was two-fold: first to perform a computational benchmark for the energies in the gas phase, followed by benchmarking the enthalpy and the Gibbs energy, including solvation and entropy, from experimental references.