A novel rhenium complex bearing a non-innocent PNP pincer ligand was prepared. This novel catalyst is active in hydrogen autotransfer reactions to form new C–C and C–N bonds. More specifically, valuable alkylations of ketones and sulfonamides with primary alcohols are herein presented. In addition, the first examples of rhenium-catalysed synthesis of pyrroles are described by dehydrogenative coupling of diols, amines and ketones.