The complexes [Ru(2,2'-dipicolylamine)(OH2)(3)](OTf)(2) and [Ru(6,6'-bis(aminomethyl)-2,2'-bipyridine)(OH2)(2)](OTf)(2) can be prepared by reaction of 2,2'-dipicolylamine or 6,6'-bis(aminomethyl)-2,2'-bipyridine with [Ru-IIIi(DMF)(6)](OTf)(3) in aqueous medium. During the reaction an in situ reduction from a paramagnetic Ru-III to a diamagnetic Ru-II-complexes occurs with one equivalent of DMF acting as the reducing agent for two ruthenium centres by its reaction with water and decomposition to dimethylammonium triflate and CO2 generating an additional equivalent of HOTf in the process. The complex solutions are active as catalysts for the hydrogenation of 2,5-hexanedione and 2,5-dimethylfuran to 2,5-hexanediol and 2,5-dimethyltetrahydrofuran with both complexes realizing very high yields (>95% combined yield of the two products with the selectivity determined as a function of added acid co-catalyst). The 2,2'-dipicolylamine complex is stable to 150 degrees C, while the 6,6'-bis(aminomethyl)-2,2'-bipyridine complex is stable to 200 degrees C allowing the in situ hydrolysis of 2,5-dimethylfuran to the 2,5-hexanedione and thus direct conversion to the same products in up to 78% combined yield. The effects of co-solvents, acid co-catalysts and temperature on catalyst activity, decomposition and stability are explored. (C) 2015 Elsevier B.V. All rights reserved.