New water-soluble iridium(I)-N-heterocyclic carbene-tertiary phosphine mixed-ligand complexes as catalysts of hydrogenation and redox isomerization

Henrietta Horváth, Ágnes Kathó, Antal Udvardy, Gábor Papp, Dorina Szikszai, Ferenc Joó

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33 Citations (Scopus)

Abstract

Seven new [Ir(NHC)(η4-cod)(L)] complexes (4-9, 11) with NHC = bmim, emim, L = Cl-, H2O, or the water-soluble phosphines mtppms-Na, mtppts-Na3, and pta were synthesized and characterized. Na2[Ir(bmim)( η4-cod)(mtppts)] (6) and [Ir(bmim)( η4-cod)(pta)]Cl (7) actively catalyzed hydrogenation of alkenoic and oxo acids in aqueous solution. These catalysts were also found to be active in the hydrogenation of highly substituted C=C bonds (such as those in methylmaleic and methylfumaric acids). The stability of 6 was significantly increased by the addition of formate or oxalate. Under hydrogen, active catalysts were formed in situ from [IrCl(bmim)( η4-cod)], [IrCl(η4-cod)(emim)], or [IrCl(η4-cod)(IMes)] and mtppts-Na3 or pta. In the presence of HCOONa, [IrCl(η4-cod)(bmim)] + mtppts-Na3 showed a TOF of 150 h-1in the hydrogenation of itaconic acid in water at 60 °C, which is the highest value determined to date for a water-soluble Ir(I) hydrogenation catalyst in an aqueous system. Both 6 and 7 selectively isomerized alk-1-en-3-ols to the corresponding methyl ketones with no need for an external reducing agent such as H2. Furthermore, Na2[Ir(bmim)( η4-cod)(mtppts)] (6) was also shown to catalytically decompose aqueous formate to H2 and bicarbonate.

Original languageEnglish
Pages (from-to)6330-6340
Number of pages11
JournalOrganometallics
Volume33
Issue number22
DOIs
Publication statusPublished - Nov 24 2014

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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