Interaction of a bulky N-heterocyclic carbene ligand with Rh(I) and Ir(I). Double C-H activation and isolation of bare 14-electron Rh(III) and Ir(III) complexes

NM Scott, R Dorta, ED Stevens, A Correa, L Cavallo, Steven Patrick Nolan

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279 Citations (Scopus)

Abstract

Reactivity and structural studies of unusual rhodium and iridium systems bearing two N-heterocyclic carbene (NHC) ligands are presented. These systems are capable of intramolecular C-H bond activation and lead to coordinatively unsaturated 16-electron complexes. The resulting complexes can be further unsaturated by simple halide abstraction, leading to 14-electron species bearing an all-carbon environment. Saturation of the vacant sites in the 16- and 14-electron complexes with carbon monoxide permits a structural comparison. DFT calculations show that these electrophilic metal centers are stabilized by pi-donation of the NHC ligands.

Original languageEnglish
Pages (from-to)3516-3526
Number of pages11
JournalJournal of the American Chemical Society
Volume127
Issue number10
DOIs
Publication statusPublished - 16 Mar 2005

Keywords

  • X-RAY CRYSTAL
  • MOLECULAR-STRUCTURE
  • ALKANE DEHYDROGENATION
  • OLEFIN HYDROGENATION
  • AGOSTIC INTERACTIONS
  • OXIDATIVE ADDITION
  • HYDRIDE COMPLEXES
  • BOND ACTIVATION
  • TERT-BUTYL
  • IRIDIUM

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