An unusual Microdomain Factor Controls Interaction of Organic Halides with the Palladium Phase and Influences Catalytic Activity in the Mizoroki‐Heck Reaction

In this work, using a combination of scanning and transmission electron microscopy (SEM and TEM), the transformations of palladium‐containing species in imidazolium ionic liquids in reaction mixtures of the Mizoroki‐Heck reaction and in related organic media are studied to understand a challenging question of the relative reactivity of organic halides as key substrates in modern catalytic technologies. The microscopy technique detects the formation of a stable nanosized palladium phase under the action of an aryl (Ar) halide capable of forming microcompartments in an ionic liquid. For the first time, the correlation between the reactivity of the aryl halide and the microdomain structure is observed: Ar‐I (well‐developed microdomains) > Ar‐Br (microphase present) > Ar‐Cl (minor amount of microphase). Previously, it is assumed that molecular level factors, namely, carbon‐halogen bond strength and the ease of bond breakage, are the sole factors determining the reactivity of aryl halides in catalytic transformations. The present work reports a new factor connected with the nature of the organic substrates used and their ability to form a microdomain structure and concentrate metallic species, highlighting the importance of considering both the molecular and microscale properties of the reaction mixtures.