162970 20251017144653.0 doi 10.3390/molecules30163398 sideral 145422 ART-2025-145422 eng Grasa, Alejandro Universidad de Zaragoza Pyridyl-Thiourea Ruthenium and Osmium Complexes: Coordination of Ligand and Application as FLP Hydrogenation Catalysts 2025 Access copy available to the general public Unrestricted Pyridyl-thiourea complexes of formula [(Cym)MCl(κ2Npy,S-H2NNS)][SbF6] (Cym = η6-p-MeC6H4iPr; H2NNS = N-(p-tolyl)-N′-(2-pyridylmethyl)thiourea); M = Ru (1), Os (2)) were synthesized by reacting the corresponding metal dimers [{(Cym)MCl}2(μ-Cl)2] with H2NNS in the presence of NaSbF6. Subsequent chloride abstraction with AgSbF6, followed by NH deprotonation using NaHCO3, afforded the cationic complexes [(Cym)M(κ3Npy,Namide,S-HNNS)][SbF6] (M = Ru (5a), (5c); M = Os (6a, 6c)) and [(Cym)M(κ2Namide,S-HNNS)][SbF6] (M = Ru (5b); M = Os (6b)). The proposed structures for the prepared compounds are based on NMR data. Complexes 5a, 5b, and 6a, 6b evolve to the thermodynamically more stable species 5c and 6c, respectively, in which the deprotonated ligand HNNS adopts a κ3Npy,Namide,S coordination mode. Complexes 5c and 6c activate H2, behaving as frustrated Lewis pair (FLP) species, and catalyze (5c and/or 6c) the hydrogenation of polar multiple bonds, including the C=N bonds of N-benzylideneaniline and quinoline, the C=C bond of methyl acrylate, and the C=O bond of 2,2,2-trifluoroacetophenone. info:eu-repo/grantAgreement/ES/DGA/E05-23R info:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00 info:eu-repo/semantics/openAccess by https://creativecommons.org/licenses/by/4.0/deed.es info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Leavey, Roisin D. Viguri, Fernando Universidad de Zaragoza (orcid)0000-0002-6160-3046 Rodríguez, Ricardo (orcid)0000-0002-8845-0174 Lamata, Pilar Universidad de Zaragoza (orcid)0000-0001-9071-563X 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 30, 16 (2025), 3398 [21 pp.] Molecules (Basel, Online) Molecules 1420-3049 2489476 http://zaguan.unizar.es/record/162970/files/texto_completo.pdf Versión publicada 2579925 http://zaguan.unizar.es/record/162970/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:162970 articulos driver 2025-10-17-14:37:13 ARTICLE