2018 Fiscal Year Annual Research Report
異種二核金属錯体と第二配位圏の遷移金属錯体による酸化触媒及びＣＨ活性化触媒の創出
| Project/Area Number |
16F16038
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| Research Institution | Okinawa Institute of Science and Technology Graduate University |
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Principal Investigator |
クスヌディノワ ジュリア 沖縄科学技術大学院大学, 錯体化学・触媒ユニット, 准教授 (90747544)
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| Co-Investigator(Kenkyū-buntansha) |
RIVADA WHEELAGHA ORESTES 沖縄科学技術大学院大学, 錯体化学・触媒ユニット, 外国人特別研究員
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| Project Period (FY) |
2016-07-27 – 2019-03-31
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| Keywords | polymetallic complex / polynucleating ligand / linear chain complex |
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| Outline of Annual Research Achievements |
During Fiscal Year 2018, the JSPS fellow Dr Orestes Rivada-Wheelaghan was involved in finalizing the research projects on the formation of heteropolymetallic complexes. Several directions were pursued:
1) Selective formation of Cu-Pd-Pd-Cu complexes was achieved using polynuclearing ligands proposed in this project. These complexes were found to react with terminal alkyne to give a binuclear Pd-Cu acetylide complex, which then undergoes C-C elimination from Pd(acetyline)(Aryl) center. This reactivity closely resembles the mechanism of the Sonogashira coupling. Our ligand platform allows to obtain model compounds that shed light on the mechanism of Sonogashira coupling as they feature Cu and Pd center in close proximity and allow to structurally characterize the intermediates. In collaboration with Agusti Lledos, we are currently finalizing DFT study of the detailed mechanism of C(sp)-C(sp2) coupling in multimetallic Cu-Pd complexes.
2) Using ligand modification, we also obtained a complex with "reversed" Pd-Cu-Cu-Pd core. Interestingly, this complex was found to be an active catalyst for gem-selective terminal alkyne dimerization at RT. However, later studies found that under reaction conditions, polymetallic core dissociates into mononuclear Cu and Pd, latter acting as a catalyst for alkyne dimerization.
3) We also finalized the project related to Ru complex with our ligand platform that features secondary coordination sphere interactions. This complex is active in catalytic benzyl alcohol acceptorless dehydrogenation.
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| Research Progress Status |
平成30年度が最終年度であるため、記入しない。
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| Strategy for Future Research Activity |
平成30年度が最終年度であるため、記入しない。
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