Molecular hydrogen and water activation by transition metal frustrated Lewis pairs containing ruthenium or osmium components: catalytic hydrogenation assays

Beard, Sophie ; Grasa, Alejandro (Universidad de Zaragoza) ; Viguri, Fernando (Universidad de Zaragoza) ; Rodríguez, Ricardo ; López, José A. (Universidad de Zaragoza) ; Lahoz, Fernando J. ; García-Orduña, Pilar ; Lamata, Pilar (Universidad de Zaragoza) ; Carmona, Daniel

Resumen: 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.

Idioma: Inglés

DOI: 10.1039/d3dt02339g

Año: 2023

Publicado en: Dalton Transactions 52, 37 (2023), 13216-13228
ISSN: 1477-9226

Factor impacto JCR: 3.5 (2023)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 13 / 44 = 0.295 (2023) - Q2 - T1

Factor impacto CITESCORE: 6.6 - Inorganic Chemistry (Q2)

Factor impacto SCIMAGO: 0.697 - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/AEI/PID2020-119512GB-I00
Financiación: info:eu-repo/grantAgreement/ES/DGA/E05-20R
Financiación: info:eu-repo/grantAgreement/ES/DGA/E05-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00

Tipo y forma: Article (PostPrint)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)