2022 Fiscal Year Final Research Report
Transition Metal Complexes Having Phosphinyl Radicals as Ligands: Functions Based on Orbital Interactions
| Project/Area Number |
19H02730
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Review Section |
Basic Section 34010:Inorganic/coordination chemistry-related
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| Research Institution | Tohoku University |
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Principal Investigator |
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| Project Period (FY) |
2019-04-01 – 2023-03-31
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| Keywords | リンラジカル / 速度論的安定化 / 遷移金属錯体 / 開殻種 / サーモクロミズム |
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| Outline of Final Research Achievements |
We have synthesized transition metal complexes with a phosphinyl radical as a ligand, and we have investigated their functionalities based on the orbital interactions between the radical ligand and the transition metals center. The properties of the pentafluorophenyl-group 11 element (Au, Ag, and Cu) complexes with one phosphinyl radical depend on the central metal, although their spins are mainly localized on the phosphorus atom. In particular, we found that the copper complex with phosphorus radical exhibits solvent-dependent thermochromism, which we attributed to the coordination of the solvent and the dimerization at low temperatures. On the other hand, the corresponding gold complex does not show thermochromism in solution. These results would contribute to the development of the open-shell transition metal complexes and their functionalities.
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| Free Research Field |
有機典型元素化学
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| Academic Significance and Societal Importance of the Research Achievements |
近年、ラジカル配位子や、ノンイノセント配位子（電子授受性を持つ配位子）を持つ遷移金属錯体が、従来の閉殻系錯体と異なる高い反応性や、配位子も触媒反応に直接関与する協働作用性、外部環境に応じた応答を示す物質群として注目を集めている。本研究課題の成果はそれに貢献する内容となっている。今回合成したリンラジカル配位11族金属錯体の性質の金属依存性はこれまで未知であり、基礎的な情報として極めて重要である。また、リンラジカル銅錯体が示したスピン多重度の変化を伴う溶媒依存性サーモクロミズムは、機能性材料としての応用が期待できるのみならず、外部環境に応じて反応性が極端に変化する錯体の創製にもつながる。
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