Catalytic Dehydrogenative C-C Coupling by a Pincer-Ligated Iridium Complex

Miles Wilklow-Marnell, Bo Li, Tian Zhou, Karsten Krogh-Jespersen, William W. Brennessel, Thomas J. Emge, Alan S. Goldman, William D. Jones

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15 Citations (Scopus)

Abstract

The pincer-iridium fragment (iPrPCP)Ir (RPCP = ?3-2,6-C6H3(CH2PR2)2) has been found to catalyze the dehydrogenative coupling of vinyl arenes to afford predominantly (E,E)-1,4-diaryl-1,3-butadienes. The eliminated hydrogen can undergo addition to another molecule of vinyl arene, resulting in an overall disproportionation reaction with 1 equiv of ethyl arene formed for each equivalent of diarylbutadiene produced. Alternatively, sacrificial hydrogen acceptors (e.g., tert-butylethylene) can be added to the solution for this purpose. Diarylbutadienes are isolated in moderate to good yields, up to ca. 90% based on the disproportionation reaction. The results of DFT calculations and experiments with substituted styrenes indicate that the coupling proceeds via double C-H addition of a styrene molecule, at β-vinyl and ortho-aryl positions, to give an iridium(III) metalloindene intermediate; this intermediate then adds a β-vinyl C-H bond of a second styrene molecule before reductively eliminating product. Several metalloindene complexes have been isolated and crystallographically characterized. In accord with the proposed mechanism, substitution at the ortho-aryl positions of the styrene precludes dehydrogenative homocoupling. In the case of 2,4,6-trimethylstyrene, dehydrogenative coupling of β-vinyl and ortho-methyl C-H bonds affords dimethylindene, demonstrating that the dehydrogenative coupling is not limited to C(sp2)-H bonds.

Original languageEnglish
Pages (from-to)8977-8989
Number of pages13
JournalJournal of the American Chemical Society
Volume139
Issue number26
DOIs
Publication statusPublished - Jul 5 2017

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Wilklow-Marnell, M., Li, B., Zhou, T., Krogh-Jespersen, K., Brennessel, W. W., Emge, T. J., Goldman, A. S., & Jones, W. D. (2017). Catalytic Dehydrogenative C-C Coupling by a Pincer-Ligated Iridium Complex. Journal of the American Chemical Society, 139(26), 8977-8989. https://doi.org/10.1021/jacs.7b03433