表題番号：2024C-493
日付：2025/03/24
研究課題Molecular Design via Quantum Mechanical-Based Simulations for Organonickel Complexes as An Effort For Biomass Utilization
| 研究者所属（当時） | 資格 | 氏名 | |
|---|---|---|---|
| （代表者） | 理工学術院 国際理工学センター（理工学術院） | 准教授 | サクティ アディチャ ウィバワ |
| （連携研究者） | Department of Chemistry, Bandung Institute of Technology | Assistant Professor | Muhamad Abdulkadir Martoprawiro |
| （連携研究者） | Department of Chemistry, Bandung Institute of Technology | Professor | I Made Arcana |
| （連携研究者） | Department of Chemistry, Bandung Institute of Technology | PhD Student | Nova Pratiwi Indriyani |
| （連携研究者） | National Research and Innovation Agency, Indonesia | Researcher | Gagus Ketut Sunnardianto |
| （連携研究者） | Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia | Assistant Professor | Shahrul Nizam Ahmad |
- 研究成果概要
- In FY 2024, we implemented our developed in-house CMMDE software for the following applications:- Furfural (FAL) to furfuryl alcohol (FOL) hydrogenation by using a nickel(0)-based catalyst. The developed method can speed up the transition state search efficiently. We proposed two pathways of furfural hydrogenation, namely, via initial coordination between the nickel complex and FAL (scheme 1) or the alcohol molecule (scheme 2). The density-functional theory (DFT) calculations revealed that the rate-determining step of FAL to FAL hydrogenation is the hydride transfer from ⍺-carbon of alcohol to the nickel atom. Our study suggests that the electronic structure around the nickel atom influences the Gibbs activation energies of the rate-determining step.- Similar reactivity indexes and analyses were performed to investigate the electronic properties of palladium-based catalysts instead of nickel-based ones. Our method successfully connects the electronic properties with the ionization potential and electron affinities of the developed catalysts.- The kinetics analysis modules in the CMMDE code were also used in unraveling the mechanism of the Suzuki-Miyaura cross-coupling reaction by using both nickel and palladium catalysts. Our study shows that the reaction barriers for C-Cl bond cleavage in phenyl chloride are 34.68 and 24.24 kJ/mol for palladium and nickel catalysts, respectively. This indicates that nickel can be a potential substitute for an expensive palladium catalyst.