This thesis deals with the development of different homogeneous PNP pincer catalysts and their application in hydrogen autotransfer reactions. Manganese, rhenium and cyclometalated ruthenium complexes were used as catalysts for the α-alkylation of ketones with alcohols, a reaction creating new C‒C bonds while producing water as sole stochiometric by-product. This reaction was used for the alkylation of a broad scope of ketones including biologically relevant compounds like hormones with various alcohols.