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Título: | Activation of H-H, HO-H, C(sp2)-H, C(sp3)-H, and RO-H bonds by transition-metal frustrated Lewis pairs based on M/N (M = Rh, Ir) couples |
Autor: | Carmona, María CSIC ORCID; Pérez, Roberto; Ferrer, Joaquina CSIC ORCID; Rodríguez, Ricardo CSIC ORCID; Passarelli, Vincenzo CSIC ORCID; Lahoz, Fernando J. CSIC ORCID; García-Orduña, Pilar CSIC ORCID; Carmona, Daniel CSIC ORCID | Fecha de publicación: | 2022 | Editor: | American Chemical Society | Citación: | Inorganic Chemistry 61(33): 13149-13164 (2022) | Resumen: | Reaction of the dimers [(Cp*MCl)2(μ-Cl)2] (Cp* = η5-C5Me5) with Ph2PCH2CH2NC(NH(p-Tolyl))2 (H2L) in the presence of NaSbF6 affords the chlorido complexes [Cp*MCl(κ2N,P-H2L)][SbF6] (M = Rh, 1; Ir, 2). Upon treatment with aqueous NaOH, solutions of 1 and 2 yield the corresponding complexes [Cp*M(κ3N,N′,P-HL)][SbF6] (M = Rh, 3; Ir, 4) in which the ligand HL presents a fac κ3N,N′,P coordination mode. Treatment of THF solutions of complexes 3 and 4 with hydrogen gas, at room temperature, results in the formation of the metal hydrido-complexes [Cp*MH(κ2N,P-H2L)][SbF6] (M = Rh, 5; Ir, 6) in which the N(p-Tolyl) group has been protonated. Complexes 3 and 4 react with deuterated water in a reversible fashion resulting in the gradual deuteration of the Cp* group. Heating at 383 K THF/H2O solutions of the complexes 3 and 4 affords the orthometalated complexes [Cp*M(κ3C,N,P-H2L-H)][SbF6] [M = Rh, 7; Ir, 8, H2L-H = Ph2PCH2CH2NC(NH(p-Tolyl))(NH(4-C6H3Me))], respectively. At 333 K, complexes 3 and 4 react in THF with methanol, primary alcohols, or 2-propanol giving the metal-hydrido complexes 5 and 6, respectively. The reaction involves the acceptorless dehydrogenation of the alcohols at a relatively low temperature, without the assistance of an external base. The new complexes have been characterized by the usual analytical and spectroscopic methods including the X-ray diffraction determination of the crystal structures of complexes 1–5, 7, and 8. Notably, the chlorido complexes 1 and 2 crystallize both as enantiopure conglomerates and as racemates. Reaction mechanisms are proposed based on stoichiometric reactions, nuclear magnetic resonance studies, and X-ray crystallography as well as density functional theory calculations. | Versión del editor: | https://doi.org/10.1021/acs.inorgchem.2c01902 | URI: | http://hdl.handle.net/10261/303517 | DOI: | 10.1021/acs.inorgchem.2c01902 | E-ISSN: | 1520-510X |
Aparece en las colecciones: | (ISQCH) Artículos |
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