A rhodium(ii)/rhodium(iii) redox couple for C-H bond amination with alkylazides: a rhodium(iii)-nitrenoid intermediate with a tetradentate [14]-macrocyclic ligand
説明
The catalytic activity of a rhodium(ii) dimer complex, [RhII(TMAA)]2 (TMAA = tetramethyltetraaza[14]annulene), in C-H amination reactions with organic azides is explored. Organic azides (N3-R) with an electron-withdrawing group such as a sulfonyl group (trisylazide; R = S(O)2iPr3C6H2 (Trs)) and a simple alkyl group (R = (CH2)4Ph, (CH2)2OCH2Ph, CH2Ph, or C6H4NO2) are employed in intra- and intermolecular C-H bond amination reactions. The spectroscopic analysis using ESI-mass and EPR spectroscopy techniques on the reaction intermediate generated from [RhII(TMAA)]2 and N3-R reveals that a rhodium(iii)-nitrenoid species is an active oxidant in the C-H bond amination reaction. DFT calculations suggest that the species can feature a radical localised nitrogen atom. The DFT calculation studies also indicate that the amination reaction involves hydrogen atom abstraction from the organic substrate R′-H by the NR moiety of 2N˙R and successive rebound of the generated organic radical intermediate R′˙ to [RhIII(NH-R)(TMAA)], giving [RhII(TMAA)] and R′-NH-R (amination product).
収録刊行物
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- Dalton Transactions
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Dalton Transactions 53 (4), 1607-1615, 2024-01-28
Royal Society of Chemistry
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詳細情報 詳細情報について
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- CRID
- 1050018218945793536
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- ISSN
- 14779234
- 14779226
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- HANDLE
- 11094/94620
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- 本文言語コード
- en
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- 資料種別
- journal article
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- データソース種別
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- IRDB