Iron-mediated coupling of carbon dioxide and ethylene: Macrocyclic metallalactones enable access to various carboxylates

Stephan M. Rummelt, Hongyu Zhong, Ilia Korobkov, Paul J. Chirik

Research output: Contribution to journalArticle

11 Scopus citations

Abstract

Treatment of (iPrPDI)Fe(N2)2 (iPrPDI, 2,6-(2,6-iPr2C6H3Nâ• CMe)2C5H3N) with CO2 and ethylene resulted in the formation of a homologous series of saturated and unsaturated iron carboxylate products, (iPrPDI)Fe(O2CR), the distribution of which depends on the ratio of the reagents. The solid-state and electronic structures of a saturated product, (iPrPDI)Fe(O2CC2H5), were elucidated. Product distributions, deuterium labeling studies, and stoichiometric experiments support initial formation of a five-membered metallalactone intermediate, which undergoes subsequent ethylene insertions to generate macrocyclic metallalactones. Competitive β-hydride elimination, CO2 insertion, or reaction with H2 determines the fate of the metallalactone, the latter accounting for formation of iron complexes with saturated carboxylates. Similar reactivity was observed upon addition of propiolactone and ethylene to (iPrPDI)Fe(N2)2, supporting C-O oxidative addition and C-C bond formation through metallacycle intermediates.

Original languageEnglish (US)
Pages (from-to)11589-11593
Number of pages5
JournalJournal of the American Chemical Society
Volume140
Issue number37
DOIs
StatePublished - Sep 19 2018

All Science Journal Classification (ASJC) codes

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

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