Dicarbonyliridium(I) complexes of pyridine ester ligands and their reactivity towards various electrophiles

Dimpi Bora, Biswajit Deb, Amy L. Fuller, Alexandra M. Z. Slawin, J. Derek Woollins, Dipak Kumar Dutta

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26 Citations (Scopus)

Abstract

The reaction of dimeric precursor [Ir(CO)(2)Cl](2) with two molar equivalent of the pyridine-ester ligands (L) like methyl picolinate (a), ethyl picolinate (b), methyl nicotinate (c), ethyl nicotinate (d), methyl isonicotinate (e) and ethyl isonicotinate (f) affords the tetra coordinated neutral complexes of the type [Ir(CO)(2)ClL] (1a-f). The single crystal X-ray structure of 1d reveals that the Ir atom occupies the centre of an approximately square planar geometry with two CO groups cis- to each other. Intermolecular C-H center dot center dot center dot O and Ir center dot center dot center dot C interactions greatly stabilize the supramolecular structure of 1d in the solid state. The oxidative addition (OA) reactions of 1a-f with different electrophiles such as CH3I, C2H5I and I-2 undergo decarbonylation of one CO group to generate the oxidized products of the type [Ir(CO)RClIL] where R = -CH3 (2a-f); -C2H5 (3a-f) and [Ir(CO)ClI2L] (4a-f). Kinetic study of the reaction of 1c-f with CH3I indicates a first order reaction which follow the order 1d > 1c > 1f > 1e. All the synthesized complexes were characterized by elemental analyses, IR, and multinuclear NMR spectroscopy. (C) 2010 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)1539-1546
Number of pages8
JournalInorganica Chimica Acta
Volume363
Issue number7
DOIs
Publication statusPublished - 20 Apr 2010

Keywords

  • Iridium(I)
  • Carbonyl complexes
  • Pyridine ester
  • X-ray crystal structure
  • Electrophiles
  • Oxidative addition
  • RHODIUM(I) CARBONYL-COMPLEXES
  • CATALYZED METHANOL CARBONYLATION
  • OXIDATIVE ADDITION-REACTIONS
  • NITROGEN-DONOR LIGANDS
  • IRIDIUM COMPLEXES
  • DICARBONYLRHODIUM(I) COMPLEXES
  • METHYL-IODIDE
  • ACETIC-ACID
  • MECHANISM

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