著作: [落合 正仁]/Suefuji Takashi/[宮本 和範]/Tada Norihiro/[後藤 了]/Shiro Motoo/Sakamoto Shigeki/Yamaguchi Kentaro/Secondary hypervalent I(III) ---O interactions: Synthesis and structure of hypervalent complexes of diphenyl-<lambda>^3-iodanes with 18-crown-6/[Journal of the American Chemical Society]
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| 種別 | 必須 | 学術論文(審査論文) | |||
|---|---|---|---|---|---|
| 言語 | 必須 | 英語 | |||
| 招待 | 推奨 | ||||
| 審査 | 推奨 | ||||
| カテゴリ | 推奨 | ||||
| 共著種別 | 推奨 | ||||
| 学究種別 | 推奨 | ||||
| 組織 | 推奨 |
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| 著者 | 必須 | ||||
| 題名 | 必須 |
(英) Secondary hypervalent I(III) ---O interactions: Synthesis and structure of hypervalent complexes of diphenyl-<lambda>^3-iodanes with 18-crown-6 |
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| 副題 | 任意 | ||||
| 要約 | 任意 |
(英) Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. (1)H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph(2)IBF(4) exclusively forms the 1:1 complex with 18C6 (binding constant K(a), 1.02 x 10(3) M(-)(1)). The binding constants decrease with the increased solvent donor ability (Gutmann's DN). Changing the heteroatom ligand from BF(4) to the less nucleophilic PF(6) and AsF(6) increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph(2)IBF(4) tends to increase in the complex stability. A linear Hammett relationship (rho = 0.59) between log K(a) and sigma(p)(+) values of substituents indicates that the diaryl-lambda(3)-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10. |
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| キーワード | 推奨 | ||||
| 発行所 | 推奨 | アメリカ化学会 | |||
| 誌名 | 必須 |
Journal of the American Chemical Society([アメリカ化学会])
(pISSN: 0002-7863, eISSN: 1520-5126)
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| 巻 | 必須 | 125 | |||
| 号 | 必須 | 3 | |||
| 頁 | 必須 | 769 773 | |||
| 都市 | 任意 | ||||
| 年月日 | 必須 | 2003年 1月 22日 | |||
| URL | 任意 | http://ci.nii.ac.jp/naid/80015791212/ | |||
| DOI | 任意 | 10.1021/ja0211205 (→Scopusで検索) | |||
| PMID | 任意 | 12526677 (→Scopusで検索) | |||
| CRID | 任意 | 1570009751824052352 | |||
| NAID | 80015791212 | ||||
| WOS | 任意 | 000180468900035 | |||
| Scopus | 任意 | ||||
| 評価値 | 任意 | ||||
| 被引用数 | 任意 | ||||
| 指導教員 | 推奨 | ||||
| 備考 | 任意 |
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