Aydemir, MuratMeric, NerminBaysal, Akin2024-04-242024-04-2420120022-328X1872-8561https://doi.org/10.1016/j.jorganchem.2012.08.031https://hdl.handle.net/11468/15722Hydrogen transfer reduction processes are attracting increasing interest from synthetic chemists in view of their operational simplicity. 3,3'-bis(diphenylphosphinoamine)-2,2'-bipyridine, (Ph2PNH)(2)C10H6N2, was prepared through a single step reaction of 3,3'-diamino-2,2'-bipyridine with diphenyl-chlorophosphine. Reaction of (Ph2PNH)(2)C10H6N2 with [Ru(eta(6)-benzene)(mu-Cl)Cl](2), [Rh(mu-Cl)(cod)](2) or [Ir(eta(5)-C5Me5)(mu-Cl)Cl](2) gave a range of new bridged dinuclear complexes (C10H6N2{NHPPh2Ru(eta(6)-benzene)Cl-2}(2)], 1, [C10H6N2{PPh2NHRh(cod)Cl}(2)], 2 and [C10H6N2{NHPPh2Ir(eta(5)-C5Me5)Cl-2}(2)], 3, respectively. All new complexes have been fully characterized by analytical and spectroscopic methods. (HP)-H-1-P-31{H-1} NMR, (HC)-H-1-C-13 HETCOR or (HH)-H-1-H-1 COSY correlation experiments were used to confirm the spectral assignments. 1, 2 and 3 are suitable catalyst precursors for the transfer hydrogenation of acetophenone derivatives. Notably [Ru((Ph2PNH)(2)C10H6N2)(eta(6)-benzene)Cl-2], 1 acts as an excellent catalyst, giving the corresponding alcohols in 98-99% yields in 10 min at 82 degrees C (TOF <= 600 h(-1)) for the transfer hydrogenation reaction in comparison to analogous rhodium or iridium complexes. This transfer hydrogenation is characterized by low reversibility under these conditions. (C) 2012 Elsevier B.V. All rights reserved.eninfo:eu-repo/semantics/closedAccessAminophosphineTransition MetalTransfer HydrogenationCatalystNmrArticle7203845WOS:0003107654000062-s2.0-8486751971910.1016/j.jorganchem.2012.08.031Q2Q2