000150738 001__ 150738
000150738 005__ 20250214153850.0
000150738 0247_ $$2doi$$a10.1021/acs.inorgchem.4c03214
000150738 0248_ $$2sideral$$a142785
000150738 037__ $$aART-2025-142785
000150738 041__ $$aeng
000150738 100__ $$aFerrer-Bru, Carlos
000150738 245__ $$aDiverse and Selective Metal–Ligand Cooperative Routes for Activating Non-Functionalized Ketones
000150738 260__ $$c2025
000150738 5060_ $$aAccess copy available to the general public$$fUnrestricted
000150738 5203_ $$aThe 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.
000150738 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E05-23R$$9info:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00$$9info:eu-repo/grantAgreement/ES/MCIU/CTQ2018-095561-BI00
000150738 540__ $$9info:eu-repo/semantics/embargoedAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000150738 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000150738 700__ $$0(orcid)0000-0003-4568-2204$$aFerrer, Joaquina$$uUniversidad de Zaragoza
000150738 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, Vincenzo
000150738 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, Fernando J.
000150738 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, Pilar
000150738 700__ $$0(orcid)0000-0003-4196-5856$$aCarmona, Daniel
000150738 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000150738 773__ $$g64, 5 (2025), 2188-2206$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000150738 8564_ $$s12185012$$uhttps://zaguan.unizar.es/record/150738/files/texto_completo.pdf$$yPostprint$$zinfo:eu-repo/date/embargoEnd/2026-01-31
000150738 8564_ $$s2705794$$uhttps://zaguan.unizar.es/record/150738/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint$$zinfo:eu-repo/date/embargoEnd/2026-01-31
000150738 909CO $$ooai:zaguan.unizar.es:150738$$particulos$$pdriver
000150738 951__ $$a2025-02-14-14:03:42
000150738 980__ $$aARTICLE