CO2 activation by metal−ligand-cooperation mediated by iridium pincer complexes

Moran Feller, Eyal Ben-Ari, Yael Diskin-Posner, David Milstein

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Herein we report the reversible activation of CO2 by the dearomatized complex [(tBuPNP*)Ir(COE)] (1) and by the aromatized complex [(tBuPNP)Ir(C6H5)] (2) via metal-ligand cooperation (MLC) (tBuPN = 2,6-bis-(di-tert-butylphosphinomethyl)pyridine; tBuPNP* = deprotonated PNP; COE = cyclooctadiene). The [1,3]-addition of CO2 to 1 and 2 is reversible at ambient temperature. While the dearomatized complex 1 reacts readily at ambient temperature with CO2 in THF or benzene, complex 2 reacts with CO2 upon heating in benzene at 80 °C or at ambient temperature in THF. The novel aromatized complex [(tBuPNP)IrCl] (10) does not react with CO2. Based on the reactivity patterns of 1, 2, and 10 with CO2, we suggest that CO2 activation via MLC takes place only via the dearomatized species, and that in the case of 2 THF plays a role as a polar solvent in facilitating formation of the dearomatized hydrido phenyl complex intermediate (complex II).

Original languageEnglish
Pages (from-to)1-11
Number of pages11
JournalJournal of Coordination Chemistry
DOIs
Publication statusAccepted/In press - May 25 2018

Fingerprint

Iridium
iridium
ambient temperature
Chemical activation
activation
Benzene
Metals
Ligands
benzene
ligands
Pyridine
metals
Temperature
pyridines
reactivity
Heating
heating

Keywords

  • carbon dioxide, CO Activation
  • Iridium complex
  • metal-ligand cooperation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

CO2 activation by metal−ligand-cooperation mediated by iridium pincer complexes. / Feller, Moran; Ben-Ari, Eyal; Diskin-Posner, Yael; Milstein, David.

In: Journal of Coordination Chemistry, 25.05.2018, p. 1-11.

Research output: Contribution to journalArticle

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N2 - Herein we report the reversible activation of CO2 by the dearomatized complex [(tBuPNP*)Ir(COE)] (1) and by the aromatized complex [(tBuPNP)Ir(C6H5)] (2) via metal-ligand cooperation (MLC) (tBuPN = 2,6-bis-(di-tert-butylphosphinomethyl)pyridine; tBuPNP* = deprotonated PNP; COE = cyclooctadiene). The [1,3]-addition of CO2 to 1 and 2 is reversible at ambient temperature. While the dearomatized complex 1 reacts readily at ambient temperature with CO2 in THF or benzene, complex 2 reacts with CO2 upon heating in benzene at 80 °C or at ambient temperature in THF. The novel aromatized complex [(tBuPNP)IrCl] (10) does not react with CO2. Based on the reactivity patterns of 1, 2, and 10 with CO2, we suggest that CO2 activation via MLC takes place only via the dearomatized species, and that in the case of 2 THF plays a role as a polar solvent in facilitating formation of the dearomatized hydrido phenyl complex intermediate (complex II).

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