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Title

Base-Promoted, Remote C−H Activation at a Cationic (η5‑C5Me5)Ir(III) Center Involving Reversible C−C Bond Formation of Bound C5Me5

AuthorsMoreno, Juan J.; Espada, María F.; Campos, Jesús ; López-Serrano, Joaquín ; Macgregor, Stuart A.; Carmona, Ernesto
Issue Date2019
PublisherAmerican Chemical Society
CitationJournal of the American Chemical Society, 141, 2205−2210 (2019)
AbstractC−H bond activation at cationic [(η5- C5Me5)Ir(PMe2Ar′)] centers is described, where PMe2Ar′ are the terphenyl phosphine ligands PMe2ArXyl 2 and PMe2ArDipp 2. Different pathways are defined for the conversion of the five-coordinate complexes [(η5-C5Me5)- IrCl(PMe2Ar′)]+, 2(Xyl)+ and 2(Dipp)+, into the corresponding pseudoallyls 3(Xyl)+ and 3(Dipp)+. In the absence of an external Brønsted base, electrophilic, remote ζ C−H activation takes place, for which the participation of dicationic species, [(η5-C5Me5)Ir- (PMe2Ar′)]2+, is proposed. When NEt3 is present, the PMe2ArDipp 2 system is shown to proceed via 4(Dipp)+ as an intermediate en route to the thermodynamic, isomeric product 3(Dipp)+. This complex interconversion involves a non-innocent C5Me5 ligand, which participates in C−H and C−C bond formation and cleavage. Remarkably, the conversion of 4(Dipp)+ to 3(Dipp)+ also proceeds in the solid state.
Publisher version (URL)http://dx.doi.org/10.1021/jacs.8b11752
URIhttp://hdl.handle.net/10261/177356
DOI10.1021/jacs.8b11752
Appears in Collections:(IIQ) Artículos
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