Reaction Mechanism of Pd-Catalyzed "CO-Free" Carbonylation Reaction Uncovered by In Situ Spectroscopy: The Formyl Mechanism.

"CO-free" carbonylation reactions, where synthesis gas (CO/H2 ) is substituted by C1 surrogate molecules like formaldehyde or formic acid, have received widespread attention in homogeneous catalysis lately. Although a broad range of organics is available via this method, still relatively little is known about the precise reaction mechanism. In this work, we used in situ nuclear magnetic resonance (NMR) spectroscopy to unravel the mechanism of the alkoxycarbonylation of alkenes using different surrogate molecules. In contrast to previous hypotheses no carbon monoxide could be found during the reaction. Instead the reaction proceeds via the C-H activation of in situ generated methyl formate. On the basis of quantitative NMR experiments, a kinetic model involving all major intermediates is built which enables the knowledge-driven optimization of the reaction. Finally, a new reaction mechanism is proposed on the basis of in situ observed Pd-hydride, Pd-formyl and Pd-acyl species.

Synthesis, aggregation-enhanced emission, polymorphism and piezochromism of TPE-cored foldamers with through-space conjugation.

A series of new folded tetraphenylethene derivatives with different substituents are stereoselectively synthesized, which exhibit interesting through-space conjugation, aggregation-enhanced emission, polymorphism and piezochromism properties.