Bringing Selectivity in H/D Exchange Reactions Catalyzed by Metal Nanoparticles through Modulation of the Metal and the Ligand Shell.

Ru and Rh nanoparticles catalyze the selective H/D exchange in phosphines using D as the deuterium source. The position of the deuterium incorporation is determined by the structure of the P-based substrates, while activity depends on the nature of the metal, the properties of the stabilizing agents, and the type of the substituent on phosphorus. The appropriate catalyst can thus be selected either for the exclusive H/D exchange in aromatic rings or also for alkyl substituents.

Selective catalytic deuteration of phosphorus ligands using ruthenium nanoparticles: a new approach to gain information on ligand coordination.

Phenyl rings in phenyl- or phenyl-alkylphosphines are selectively deuterated at the ortho position using Ru/PVP nanoparticles, while are fully reduced in the case of arylphosphine oxide derivatives and do not react in the case of arylphosphite. This different behavior provides information about the coordination mode of each ligand.