The main “molecular” physicochemical aspects involved in the catalytic applications of “soluble” transition metal nanoparticles in ionic liquids are used to explain their properties. In particular, a special view on the concepts of coordination catalysis is used to describe the properties of these nanoscale catalysts in solution as well as their scope and limitations in multiphase catalysis.

A critical overview is presented on the use of charged tagged ligands (CTLs) as immobilising agents in organometallic catalysis and as probes for studying mechanisms through electrospray ionisation mass spectrometry (ESI-MS) based on the most recent literature.

The selectivity of the hydrogenation of 1,3-cyclohexadiene and 2-pentyne by Pd nanoparticles in an ionic liquid can be modulated by the addition of N- or P-containing ionophilic ligands.

A system based on copper/1,10‐phenanthroline efficiently promotes the coupling between phenols or pyrazole with (E)‐bromostilbene. (E)‐1‐Aryloxy‐1,2‐diphenylethenes were obtained from the coupling with phenols in good to excellent yields (69–90%). The exception was the reaction involving a phenol containing an electron‐withdrawing cyano group that required a longer reaction time and gave only 49% yield. Kinetic studies indicated the participation of the vinyl halide in the rate‐determining step. Under the conditions employed, the activation of the vinyl halide via a radical pathway was discarded using a radical scavenger test. By using an ionically‐tagged 1,10‐phenanthroline derivative as the ligand, various copper‐based ions were detected through ESI(+)‐MS. These ions suggested that formation of the active species [phenCuOAr(HOAr)2] precedes the vinyl halide activation.

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