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Structure-Activity Relationships in Ru(II)-Protic-NHC Complexes: β- Versus γ-Substituent Effects on Formic Acid

Ekta Yadav1, Shambhu Nath1, Achena Saha1

  • 1Department of Chemistry, Indian Institute of Technology Indore, Indore, Madhya Pradesh, India.

Chemistry, an Asian Journal
|February 8, 2026
PubMed
Summary
This summary is machine-generated.

New ruthenium complexes catalyze formic acid dehydrogenation (FADH) efficiently. The β-NH group enhances activity, while γ-NH impacts it negatively, offering insights into catalyst design for FADH and subsequent hydrogenation reactions.

Keywords:
formic acid dehydrogenationhydrogen productionionic liquidprotic NHCruthenium

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Area of Science:

  • Organometallic Chemistry
  • Catalysis
  • Green Chemistry

Background:

  • Formic acid dehydrogenation (FADH) is crucial for hydrogen storage and generation.
  • Ruthenium (Ru) complexes with N-heterocyclic carbenes (NHCs) are promising FADH catalysts.
  • Understanding substituent effects in Ru-NHC complexes is key for optimizing catalytic performance.

Purpose of the Study:

  • To synthesize and evaluate new Ru(II)-protic-NHC complexes for FADH.
  • To systematically investigate the influence of β- and γ-substituents on FADH activity.
  • To explore the application of generated gases in hydrogenation and CO2 capture.

Main Methods:

  • Synthesis of novel Ru(II)-protic-NHC complexes.
  • Catalytic evaluation of complexes for FADH under various conditions (base-assisted, ionic liquid).
  • Mechanistic studies using NMR and control experiments.

Main Results:

  • All synthesized complexes showed significant catalytic activity in FADH.
  • Complex Ru1 demonstrated exceptional performance in ionic liquid (TON=65,000, TOF=4300 h⁻¹).
  • Mechanistic studies revealed distinct pathways for base-assisted vs. ionic liquid catalysis.
  • The β-NH moiety enhanced activity, while the γ-NH group showed a detrimental effect.

Conclusions:

  • The β-NH group is beneficial for FADH catalysis, whereas the γ-NH group is detrimental.
  • Catalysis proceeds via protic-NHC pathway under base-assisted conditions and anionic-NHC intermediates in ionic liquids.
  • The H2/CO2 mixture produced is suitable for alkene hydrogenation, demonstrating practical application.