000128028 001__ 128028
000128028 005__ 20250210083428.0
000128028 0247_ $$2doi$$a10.1039/d3dt02339g
000128028 0248_ $$2sideral$$a135121
000128028 037__ $$aART-2023-135121
000128028 041__ $$aeng
000128028 100__ $$aBeard, Sophie
000128028 245__ $$aMolecular hydrogen and water activation by transition metal frustrated Lewis pairs containing ruthenium or osmium components: catalytic hydrogenation assays
000128028 260__ $$c2023
000128028 5060_ $$aAccess copy available to the general public$$fUnrestricted
000128028 5203_ $$aThe 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.
000128028 536__ $$9info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00$$9info:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00$$9info:eu-repo/grantAgreement/ES/DGA/E05-23R$$9info:eu-repo/grantAgreement/ES/DGA/E05-20R$$9info:eu-repo/grantAgreement/ES/AEI/PID2020-119512GB-I00
000128028 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000128028 590__ $$a3.5$$b2023
000128028 592__ $$a0.697$$b2023
000128028 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b13 / 44 = 0.295$$c2023$$dQ2$$eT1
000128028 593__ $$aInorganic Chemistry$$c2023$$dQ1
000128028 594__ $$a6.6$$b2023
000128028 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000128028 700__ $$aGrasa, Alejandro$$uUniversidad de Zaragoza
000128028 700__ $$0(orcid)0000-0002-6160-3046$$aViguri, Fernando$$uUniversidad de Zaragoza
000128028 700__ $$0(orcid)0000-0002-8845-0174$$aRodríguez, Ricardo
000128028 700__ $$0(orcid)0000-0003-4500-1974$$aLópez, José A.$$uUniversidad de Zaragoza
000128028 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, Fernando J.
000128028 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, Pilar
000128028 700__ $$0(orcid)0000-0001-9071-563X$$aLamata, Pilar$$uUniversidad de Zaragoza
000128028 700__ $$0(orcid)0000-0003-4196-5856$$aCarmona, Daniel
000128028 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000128028 773__ $$g52, 37 (2023), 13216-13228$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000128028 8564_ $$s2795573$$uhttps://zaguan.unizar.es/record/128028/files/texto_completo.pdf$$yPostprint
000128028 8564_ $$s1031312$$uhttps://zaguan.unizar.es/record/128028/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000128028 909CO $$ooai:zaguan.unizar.es:128028$$particulos$$pdriver
000128028 951__ $$a2025-02-10-08:31:24
000128028 980__ $$aARTICLE