Isomerization of a cationic (η5-C5Me5)Ir(III) complex involving remote C–C and C–H bond formation

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)
50 Downloads (Pure)


The reactivity of an unsaturated, cationic (C5Me5)Ir(III) complex (2(Xyl)+) bearing the xylyl-substituted terphenyl phosphine PMe2ArXyl2 (ArXyl2 = C6H3-2,6-(C6H3-2,6-Me2)2) towards triethylamine (NEt3) is studied and compared to our previous investigations based on the related complex 2(Dipp)+ containing the bulkier phosphine PMe2ArDipp2 (ArDipp2 = C6H3-2,6-(C6H3-2,6-iPr2)2). Low-temperature multinuclear NMR studies support the formation of a C–C bond between the deprotonated C5Me5 ligand and a flanking xylyl ring of the phosphine, which becomes dearomatized (complex 4(Xyl)+). Interestingly, this complex presents divergent reactivity relative to the bulkier diisopropylphenyl counterpart, undergoing formal addition of HCl to yield complex 5(Xyl)+, isomeric to the starting complex 2(Xyl)+. These transformations are rationalized by means of Density Functional Theory (DFT) calculations.

Original languageEnglish
Article number115363
Early online date14 Jul 2021
Publication statusPublished - 1 Oct 2021


  • C5Me5
  • DFT
  • Iridium
  • Organometallic
  • Terphenyl phosphine

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


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