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Polaritonic chemistry is emerging as a powerful approach to modifying the properties and reactivity of molecules and materials. However, probing how the electronics and dynamics of molecular systems change under strong coupling has been challenging due to the narrow range of spectroscopic techniques that can be applied in situ. Here we develop microfluidic optical cavities for vibrational strong coupling (VSC) that are compatible with nuclear magnetic resonance (NMR) spectroscopy using standard liquid NMR tubes. VSC is shown to influence the equilibrium between two conformations of a molecular balance sensitive to London dispersion forces, revealing an apparent change in the equilibrium constant under VSC. In all compounds studied, VSC does not induce detectable changes in chemical shifts, J-couplings, or spin-lattice relaxation times. This unexpected finding indicates that VSC does not substantially affect molecular electron density distributions, and in turn has profound implications for the possible mechanisms at play in polaritonic chemistry under VSC and suggests that the emergence of collective behavior is critical., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Isobutanal is a high value bulk material that, in principle, could be produced with 100 % atom-economy by isoselective hydroformylation of propylene with syngas. However, leading industrial Rh- and Co-catalyzed hydroformylation methods preferentially form n-butanal over the iso-product, and methods offering isoselectivity remain underdeveloped. Here we report an iodide-assisted Pd-catalyzed hydroformylation of propylene that produces isobutanal with unprecedented levels of selectivity. The method involves PdI 2 , simple alkyl monophosphines, such as tricyclohexylphosphine, and common green solvents, enabling the title reaction to occur with isoselectivity in up to 50 : 1 iso/n product ratios under industrially relevant conditions (80-120 °C). The catalytic and preliminary mechanistic experiments indicate a key role of the iodide anions in both the catalytic activity and the isoselectivity., (© 2022 Wiley-VCH GmbH.)