Diverse and Selective Metal–Ligand Cooperative Routes for Activating Non-Functionalized Ketones

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

Resumen: The rhodium and iridium complexes [Cp*M(κ3N,N′,N″-L)][SbF6] (Cp* = η5-C5Me5; M = Rh, 1; Ir, 2; HL = pyridinyl-amidine ligand) exhibit three different cooperative metal–ligand reactivity modes when interacting with nonfunctionalized ketones. With the methyl ketones CH3COR (R = CH3, Ph, CF3), activation of the ketone methyl C(sp3)–H bond yields ketonyl compounds of formula [Cp*M(CH2COR)(κ2N,N′-HL)][SbF6]. With the ketones (CF3)2CO and CF3COPh, the complexes add to the C═O double bond of the ketone. The addition of the iridium compound 2 occurs across the metal atom and the exocyclic carbon of the dearomatized pyridinyl moiety, and that of the rhodium analogue 1 takes place through the rhodium atom and the exocyclic methylene carbon of the Cp* ligand of the intermediate fulvene complex. In the rhodium case, the resulting metal-alkoxide derivative evolves to give rise to rhodium derivatives containing up to four added ketone molecules. In all of these processes, no additives are required, rendering them atom 100% efficient procedures for bond activation. From a mechanistic point of view, DFT calculation reveals that the diverse and selective behavior of 1 and 2 toward ketones can be explained by invoking three different intermediates, each driving the process through distinct reaction pathways.

Idioma: Inglés

DOI: 10.1021/acs.inorgchem.4c03214

Año: 2025

Publicado en: Inorganic Chemistry 64, 5 (2025), 2188-2206
ISSN: 0020-1669

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/MCIU/CTQ2018-095561-BI00

Tipo y forma: Article (PostPrint)

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