Journal
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 899, Issue -, Pages -Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2019.120892
Keywords
CO2 hydrogenation; Homogeneous catalysis; alpha-diimine complexes; Mechanistic studies; DFT calculations
Categories
Funding
- South Africa's National Research Fund (NRF)
- World Academy of Sciences (TWAS) [99978, 117989]
- Technology and Human Resource for Industry Programme (THRIP) [THRIP/58/30/11/2017]
- Sasol SA Ltd (University Collaboration Programme)
- University of Johannesburg's Division of Internationalization (Study Abroad Programme)
- UJ Centre for Synthesis Catalysis
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The conversion of CO2 into valuable chemicals has been of major interest because it is cheap and readily available. The concept of reducing CO2 pollution via its utilization into valuable products has inspired us to synthesise novel 4,4'-((1Z)-butane-2,3-diylidenebis(azanylylidene))dibenzoic acid (L) metal complexes {[(L)Ru-II] (C1), [(L)Rh-III] (C2), [(L]Ir-III (C3)} complexes for catalytic hydrogenation of CO2. The alpha-diimine metal complexes (C1-C3) were characterised using several analytical techniques, including: NMR spectroscopy and single crystal X-ray crystallography. In a mixture of THF/H2O and a base, all three catalyst precursors were able to hydrogenate CO2 cleanly to formate as a product. However, the best combination of catalyst precursor and a base was C1 and DBU that selectively produced formate at a moderate temperature of 120 degrees C and at 60 bar. The best productivity under these conditions is TOF of 35 h(-1) within 2 h and a TON of 322. This work is significant because it provides a one-step synthesis for formate from CO2 using alpha-diimine-based complexes which can be synthesised in a one-step reaction. The density functional theory calculations on C1 supports that Ru-H is the active species in the process of CO2 hydrogenation to formate with the insertion of the CO2 to Ru-H being the rate determining step. (C) 2019 Elsevier B.V. All rights reserved.
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