2017 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 WHEELAGHAN 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 | linear chain complex / EMAC / polymetallic complex / multicopper complex / dynamic ligand / polynucleating ligand |
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| Outline of Annual Research Achievements |
We have synthesized a diverse series of polynucleating ligands for stabilization of polynuclear complexes containing 2nd and 3rd row transition metals (Pd, Pt, Ru) as well as first row transition metals (e.g. Cu). In 2017 we focused on naphthyridinone-based dynamic ligand scaffold that contain (a) hemilabile chelating group such as mono- or bis-picolylamine unit and (b) naphthyrinone framework that allows variable denticity binding to 1-3 metal centers. Such dynamic ligand scaffold allowed stabilization of Cu(I) linear chain complexes that can selectively and reversibly interconvert between mono-, di-, tri- and tetra-metallic species. Reversibility of linear chain construction and deconstruction has not been demonstrated prior to this study and it is controlled by stoichiometry or solvent.
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| Current Status of Research Progress |
Current Status of Research Progress
1: Research has progressed more than it was originally planned.
Reason
The current study progressed more than initially expected as the unusual ability of the complexes to reversibly construct and deconstruct metal chains was discovered, not only static formation of metal chains of defined length as commonly reported in the previous literature. Such unique property is due to presence of hemilabile chelating group and variable denticity framework and this finding gives important insights into development of dynamic scaffolds not only for homopolymetallic, but also for heterobimetallic complexes and potentially gives way to use such complexes as molecular switches.
Indeed, we applied this strategy to synthesize selectively Cu-Pd-Pd-Cu and Pd-Cu-Cu-Pd chain complexes using different chelating groups, with preliminary results reported at the annual CSJ meeting.
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| Strategy for Future Research Activity |
In 2018 we plan to finalize and publish the following projects:
a)Selective synthesis of heterobimetallic tetra- and pentanuclear Cu/Pd complexes and their reactivity in Sonogashira coupling. Preliminary results show that these complexes are active in terminal alkyne activation with several intermediates isolated;
b)Synthesis of binuclear Cu/Pt complexes featuring agostic interaction of Cu center with Pt-Me ligand and their implications in transmetalation;
c)Synthesis of Ru dimeric complexes and their reactivity with water, alcohol and catalytic reactivity in benzylic alcohol dehydrogenation and H/D exchange. Preliminary results show that while dimeric Ru complexes are initially formed, they break into monomers in protic solvents and selectively convert benzylic alcohols into aldehydes.
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| Remarks |
First link above is for highlight intended for the general audience to disseminate the results to general public. Second link contains a brief overview of research groups' results.
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