Well-Stabilized but Strained Frustrated Lewis Pairs Based on Rh/N and Ir/N Couples

Ferrer, Carlos ; Ferrer, Joaquina (Universidad de Zaragoza) ; Passarelli, Vincenzo ; Lahoz Diaz, Fernando J. ; García-Orduña, Pilar ; Carmona, Daniel

Resumen: The dimers (CpMCl)2(µ-Cl)2] (Cp* = 5-C5Me5) react with N-pyridin-2-ylmethyl-N', N¿-bis-(2, 6-diisopropylphenyl)guanidine (H2L) in the presence of NaSbF6, giving rise to chlorido compounds of formula CpMCl(¿2N, N'-H2L)]SbF6] (M = Rh, 1; Ir, 2), in which the guanidine ligand adopts a ¿2N, N' chelate coordination mode. Compounds 1 and 2 react with NaOH, rendering the complexes CpM(¿3N, N', N¿-HL)]SbF6] (M = Rh, 3; Ir, 4), in which the HL ligand exhibits a fac ¿3N, N', N¿ coordination. Complexes 3 and 4 activate the H-H and O-H bonds of dihydrogen and water. The hydrido complex CpIrH(¿2N, N'-H2L)]SbF6] (6) was isolated from the reaction of the iridium complex 4 with H2. In the reaction of the rhodium complex 3 with D2O, its Cp* ligand is gradually and reversibly deuterated. A plausible mechanism for this H/D exchange is proposed. The new complexes have been characterized by analytical and spectroscopic means, including the determination of the crystal structures of the compounds 1-4 and 6 by X-ray diffractometric methods. ©

Idioma: Inglés

DOI: 10.1021/acs.organomet.2c00172

Año: 2022

Publicado en: Organometallics 41, 11 (2022), 1445-1453
ISSN: 0276-7333

Factor impacto JCR: 2.8 (2022)

Categ. JCR: CHEMISTRY, ORGANIC rank: 16 / 52 = 0.308 (2022) - Q2 - T1
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 16 / 42 = 0.381 (2022) - Q2 - T2

Factor impacto CITESCORE: 6.6 - Chemistry (Q1)

Factor impacto SCIMAGO: 0.868 - Inorganic Chemistry (Q1) - Physical and Theoretical Chemistry (Q1) - Organic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00
Financiación: info:eu-repo/grantAgreement/ES/MINECO/PGC2018-095561-B-I00

Tipo y forma: Article (Published version)

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