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Fluxional Interconversion of Divalent Palladium Complexes Having NSNSN Ligands between Flexible SNS and Rigid NNN-Coordinated Structures
http://hdl.handle.net/10935/3478
http://hdl.handle.net/10935/3478b3059b1a-77c9-411a-908a-a59868e6cf69
| 名前 / ファイル | ライセンス | アクション |
|---|---|---|
AA12303060_V42_pp14844-14855.pdf
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| アイテムタイプ | default_学術雑誌論文 / Journal Article(1) | |||||||||||
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| タイトル | ||||||||||||
| タイトル | Fluxional Interconversion of Divalent Palladium Complexes Having NSNSN Ligands between Flexible SNS and Rigid NNN-Coordinated Structures | |||||||||||
| 言語 | en | |||||||||||
| 言語 | ||||||||||||
| 言語 | eng | |||||||||||
| キーワード | ||||||||||||
| 言語 | en | |||||||||||
| 主題Scheme | Other | |||||||||||
| 主題 | Divalent Palladium Complexes | |||||||||||
| キーワード | ||||||||||||
| 言語 | en | |||||||||||
| 主題Scheme | Other | |||||||||||
| 主題 | Flexible SNS | |||||||||||
| キーワード | ||||||||||||
| 言語 | en | |||||||||||
| 主題Scheme | Other | |||||||||||
| 主題 | Fluxional Interconversion | |||||||||||
| キーワード | ||||||||||||
| 言語 | en | |||||||||||
| 主題Scheme | Other | |||||||||||
| 主題 | NSNSN | |||||||||||
| キーワード | ||||||||||||
| 言語 | en | |||||||||||
| 主題Scheme | Other | |||||||||||
| 主題 | Rigid NNN-Coordinated Structures | |||||||||||
| 資源タイプ | ||||||||||||
| 資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||||||||
| 資源タイプ | journal article | |||||||||||
| 著者 |
河田,有未
× 河田,有未
× 片岡,靖隆× 浦,康之 |
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| 抄録 | ||||||||||||
| 内容記述タイプ | Abstract | |||||||||||
| 内容記述 | Mono- and dicationic divalent palladium complexes having 2,6-bis(N-heteroarylsulfanylmethyl)pyridine ligands (NSNSN ligands) were synthesized and characterized. The NSNSN ligands were fixed in a rac-SNS tridentate coordination mode in the solid state, while the equilibria among meso-SNS, rac-SNS, and NNN isomers were observed in solution. The equilibrium between the SNS and NNN isomers could be modulated by temperature, as well as by the steric and electronic factors of the NSNSN and monodentate ligands. Lowering the temperature tended to make NNN isomers more predominant compared with SNS isomers. On the other hand, the steric demand between the ligands in the complexes shifted the equilibrium from NNN to SNS isomers. Introduction of pyridyl groups instead of pyrimidyl groups as N-heteroarenes also shifted the equilibrium to SNS isomers. DFT calculation indicated rapid ring inversion of the metallacycle moieties and relatively slow S-inversion in the SNS isomers, a result that was in good agreement with the experimentally observed dynamic behaviors. Both the experimental and theoretical results revealed that the SNS isomers had flexible structures in solution, whereas the NNN isomers were rigid and less dynamic. The mechanistic pathways for interconversion between SNS and NNN isomers were also calculated. Such calculations indicated that a pathway featuring a relatively unstable, distorted ax-SNN intermediate was plausible. The intermediate had a N-heteroarene on the coordinated sulfur atom at an axial position. | |||||||||||
| 言語 | en | |||||||||||
| 書誌情報 |
en : Dalton transactions 巻 42, p. 14844-14855, 発行日 2013-08-29 |
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| 出版者 | ||||||||||||
| 出版者 | Royal Society of Chemistry | |||||||||||
| 言語 | en | |||||||||||
| ISSN | ||||||||||||
| 収録物識別子タイプ | PISSN | |||||||||||
| 収録物識別子 | 1477-9226 | |||||||||||
| 書誌レコードID | ||||||||||||
| 識別子タイプ | NCID | |||||||||||
| 関連識別子 | AA12303060 | |||||||||||
| DOI | ||||||||||||
| 関連タイプ | isVersionOf | |||||||||||
| 識別子タイプ | DOI | |||||||||||
| 関連識別子 | https://doi.org/10.1039/C3DT51592C | |||||||||||
| 関連名称 | 10.1039/C3DT51592C | |||||||||||
| 著者版フラグ | ||||||||||||
| 出版タイプ | AM | |||||||||||
| 出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa | |||||||||||
