The synthesis of ruthenium nanoparticles (RuNPs) using secondary phosphine oxides (SPOs) as ligands is reported. These easily accessible ligands allow the formation of small nanoparticles in the size range of 1-2 nm which display a high efficiency for hydrogenation of aromatics with TOFs up to 2700 mol h À1 .Scheme 1 SPOs tautomeric equilibrium, chelate formation, and heterolytic cleavage of H 2 .Scheme 2 Secondary phosphine oxides used.

Ligands behaving badly: A series of hindered biaryl phosphine compounds are used as ligands in rhodium‐ catalyzed hydroformylation. In situ analysis of the resultant catalysts under operating conditions shows that the ligands are dissociated under high pressures of syngas, thereby creating an unselective rhodium catalyst for the hydroformylation.

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