128028 20250210083428.0 doi 10.1039/d3dt02339g sideral 135121 ART-2023-135121 eng Beard, Sophie Molecular hydrogen and water activation by transition metal frustrated Lewis pairs containing ruthenium or osmium components: catalytic hydrogenation assays 2023 Access copy available to the general public Unrestricted The transition metal frustrated Lewis pair compounds [(Cym)M(κ3S,P,N-HL1)][SbF6] (Cym = η6-p-MeC6H4iPr; H2L1 = N-(p-tolyl)-N′-(2-diphenylphosphanoethyl)thiourea; M = Ru (5), Os (6)) have been prepared from the corresponding dimer [{(Cym)MCl}2(μ-Cl)2] and H2L1 by successive chloride abstraction with NaSbF6 and AgSbF6 and NH deprotonation with NaHCO3. Complexes 5 and 6 and the previously reported phosphano–guanidino compounds [(Cym)M(κ3P,N,N′-HL2)][SbF6] [H2L2 = N,N′-bis(p-tolyl)-N′′-(2-diphenylphosphanoethyl) guanidine; M = Ru (7), Os (8)] and pyridinyl–guanidino compounds [(Cym)M(κ3N,N′,N′′-HL3)][SbF6] [H2L3 = N,N′-bis(p-tolyl)-N′′-(2-pyridinylmethyl) guanidine; M = Ru (9), Os (10)] heterolytically activate H2 in a reversible manner affording the hydrido complexes [(Cym)MH(H2L)][SbF6] (H2L = H2L1; M = Ru (11), Os (12); H2L = H2L2; M = Ru (13), Os (14); H2L = H2L3; M = Ru (15), Os (16)). DFT calculations carried out on the hydrogenation of complex 7 support an FLP mechanism for the process. Heating 9 and 10 in methanol yields the orthometalated complexes [(Cym)M(κ3N,N′,C-H2L3-H)][SbF6] (M = Ru (17), Os (18)). The phosphano–guanidino complex 7 activates deuterated water in a reversible fashion, resulting in the gradual deuteration of the three cymene methyl protons through sequential C(sp3)–H bond activation. From DFT calculations, a metal–ligand cooperative reversible mechanism that involves the O–H bond activation and the formation of an intermediate methylene cyclohexenyl complex has been proposed. Complexes 5–10 catalyse the hydrogenation of the C[double bond, length as m-dash]C double bond of styrene and a range of acrylates, the C[double bond, length as m-dash]O bond of acetophenone and the C[double bond, length as m-dash]N bond of N-benzylideneaniline and quinoline. The C[double bond, length as m-dash]C double bond of methyl acrylate adds to catalyst 9, affording complex 19 in which a new ligand exhibiting a fac κ3N,N′,C coordination mode has been incorporated. info:eu-repo/grantAgreement/ES/AEI/PID2020-119512GB-I00 info:eu-repo/grantAgreement/ES/DGA/E05-20R info:eu-repo/grantAgreement/ES/DGA/E05-23R info:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00 info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00 info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 3.5 2023 CHEMISTRY, INORGANIC & NUCLEAR 13 / 44 = 0.295 2023 Q2 T1 0.697 2023 Inorganic Chemistry 2023 Q1 6.6 2023 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Grasa, Alejandro Universidad de Zaragoza Viguri, Fernando Universidad de Zaragoza (orcid)0000-0002-6160-3046 Rodríguez, Ricardo (orcid)0000-0002-8845-0174 López, José A. Universidad de Zaragoza (orcid)0000-0003-4500-1974 Lahoz, Fernando J. (orcid)0000-0001-8054-2237 García-Orduña, Pilar (orcid)0000-0002-7063-1292 Lamata, Pilar Universidad de Zaragoza (orcid)0000-0001-9071-563X Carmona, Daniel (orcid)0000-0003-4196-5856 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 52, 37 (2023), 13216-13228 Dalton Trans. Dalton Transactions 1477-9226 2795573 http://zaguan.unizar.es/record/128028/files/texto_completo.pdf Postprint 1031312 http://zaguan.unizar.es/record/128028/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:128028 articulos driver 2025-02-10-08:31:24 ARTICLE