The catalytic activity of a series of Ru-PNP pincer ligand complexes was studied in the direct amination of alcohols with ammonia. It turned out that all complexes of PNP ligands bearing a secondary amine showed no activity in this hydrogen-shuttling reaction sequence, while all complexes of homologous ligands bearing a tertiary amine gave active catalysts. Further comparative studies on catalysts bearing an acridine-based PNP pincer ligand and a PNP ligand of the Xantphos family provided valuable mechanistic insight that led to the design of a highly active catalyst. It appears that in the group of ligands studied here only ligands that do not form stable Ru-amido complexes are active alcohol amination catalysts.