Probing the Effect of Heterocycle-bonding in PNX-type Ruthenium Pre-catalysts for Reactions Involving H2

A series of ruthenium(ii) complexes with three novel PNX-type pincer ligands is reported, in which X denotes a heterocyclic donor group (PNX = Ph2PCH2CH2N(H)CH2-X, X = 2-pyridyl, 2-furanyl, 2-thiophenyl or 2-pyrrolyl). The reaction of [(Ph3P)3RuCl2] with one equivalent of ligand leads to the trans-dichloro complexes [(PNX)RuCl2(PPh3)] (1-4) for all ligands, whereas the complexation of [(Ph3P)3Ru(H)(Cl)(CO)] results in different types of complexes. The variation of the heterocyclic donor group is in line with different binding properties and a labilization of this group. Investigations on the catalytic activity of different types of ruthenium(ii) complexes in hydrogenation and dehydrogenation reactions reveal that more labile bound heterocycle donors result in a decrease of catalytic productivity and activity.