| 研究課題/領域番号 |
16F16038
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| 研究機関 | 沖縄科学技術大学院大学 |
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研究代表者 |
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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| 研究分担者 |
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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| 研究期間 (年度) |
2016-07-27 – 2019-03-31
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| キーワード | linear chain complex / EMAC / polymetallic complex / multicopper complex / dynamic ligand / polynucleating ligand |
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| 研究実績の概要 |
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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| 現在までの達成度 (区分) |
現在までの達成度 (区分)
1: 当初の計画以上に進展している
理由
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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| 今後の研究の推進方策 |
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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| 備考 |
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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