Base-Promoted, Remote C-H Activation at a Cationic (n 5 -C 5 Me 5 )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C 5 Me 5

Juan J. Moreno, María F. Espada, Jesús Campos, Joaquín López-Serrano, Stuart A. Macgregor*, Ernesto Carmona

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Citations (Scopus)

Abstract

C-H bond activation at cationic [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] centers is described, where PMe 2 Ar′ are the terphenyl phosphine ligands PMe 2 Ar Xyl 2 and PMe 2 Ar Dipp 2 . Different pathways are defined for the conversion of the five-coordinate complexes [(n 5 -C 5 Me 5 )IrCl(PMe 2 Ar′)] + , 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, [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] 2+ , is proposed. When NEt 3 is present, the PMe 2 Ar Dipp 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 C 5 Me 5 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.

Original languageEnglish
JournalJournal of the American Chemical Society
Early online date25 Jan 2019
DOIs
Publication statusPublished - 13 Feb 2019

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