{"title":"氨基硼烷与等电子/等结构季烷基铵阳离子在水溶液中的主客体络合作用","authors":"Mona A Gamal-Eldin, D. Macartney","doi":"10.1155/2019/8124696","DOIUrl":null,"url":null,"abstract":"<jats:p>The host-guest complexation of six amine boranes (R<jats:sub>3</jats:sub>NBH<jats:sub>3</jats:sub>) by the macrocyclic host molecule cucurbit<mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\" id=\"M1\"><mml:mo stretchy=\"false\">[</mml:mo><mml:mn fontstyle=\"italic\">7</mml:mn><mml:mo stretchy=\"false\">]</mml:mo></mml:math>uril (CB<mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\" id=\"M2\"><mml:mo stretchy=\"false\">[</mml:mo><mml:mn fontstyle=\"italic\">7</mml:mn><mml:mo stretchy=\"false\">]</mml:mo></mml:math>) in aqueous solution has been investigated using <jats:sup>1</jats:sup>H and <jats:sup>11</jats:sup>B NMR spectroscopy. The limiting complexation-induced <jats:sup>1</jats:sup>H and <jats:sup>11</jats:sup>B chemical shift changes indicate that the amine boranes are included in the hydrophobic cavity of the host molecule. The host-guest stability constants for neutral <mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\" id=\"M3\"><mml:mrow><mml:mfenced open=\"{\" close=\"\" separators=\"|\"><mml:mrow><mml:mo> </mml:mo></mml:mrow></mml:mfenced></mml:mrow></mml:math>R<jats:sub>3</jats:sub>NBH<jats:sub>3</jats:sub><jats:italic>∙</jats:italic>CB<mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\" id=\"M4\"><mml:mo stretchy=\"false\">[</mml:mo><mml:mn fontstyle=\"italic\">7</mml:mn><mml:mo stretchy=\"false\">]</mml:mo><mml:mfenced open=\"\" close=\"}\" separators=\"|\"><mml:mrow><mml:mo> </mml:mo></mml:mrow></mml:mfenced></mml:math> complexes (in the range of 10<jats:sup>5</jats:sup>-10<jats:sup>7</jats:sup><mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\" id=\"M5\"><mml:mrow><mml:msup><mml:mrow><mml:mi mathvariant=\"normal\">M</mml:mi></mml:mrow><mml:mrow><mml:mtext>-</mml:mtext><mml:mn mathvariant=\"normal\">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math>) have been determined by <jats:sup>1</jats:sup>H NMR competition experiments and are compared with the corresponding values for the isoelectronic/isostructural <mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\" id=\"M6\"><mml:mrow><mml:mfenced open=\"{\" close=\"\" separators=\"|\"><mml:mrow><mml:mo> </mml:mo></mml:mrow></mml:mfenced></mml:mrow></mml:math>R<jats:sub>3</jats:sub>NCH<jats:sub>3</jats:sub><jats:italic>∙</jats:italic>CB<mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\" id=\"M7\"><mml:mo stretchy=\"false\">[</mml:mo><mml:mn fontstyle=\"italic\">7</mml:mn><mml:mo stretchy=\"false\">]</mml:mo><mml:msup><mml:mrow><mml:mfenced open=\"\" close=\"}\" separators=\"|\"><mml:mrow><mml:mo> </mml:mo></mml:mrow></mml:mfenced></mml:mrow><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math> complexes. Ammonia borane (H<jats:sub>3</jats:sub>NBH<jats:sub>3</jats:sub>) does not form a host-guest complex with CB<mml:math xmlns:mml=\"http://www.w3.org/1998/Math/MathML\" id=\"M8\"><mml:mo stretchy=\"false\">[</mml:mo><mml:mn fontstyle=\"italic\">7</mml:mn><mml:mo stretchy=\"false\">]</mml:mo></mml:math>. The trends in the host-guest stability constant with the guest molar volume are examined, and the stability is ascribed to the hydrophobic effect (packing coefficient) and quadrupole-dipole interactions.</jats:p>","PeriodicalId":12816,"journal":{"name":"Heteroatom Chemistry","volume":" ","pages":""},"PeriodicalIF":1.1000,"publicationDate":"2019-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1155/2019/8124696","citationCount":"4","resultStr":"{\"title\":\"Host-Guest Complexations of Amine Boranes and Isoelectronic/Isostructural Quaternary Alkylammonium Cations by Cucurbit[7]uril in Aqueous Solution\",\"authors\":\"Mona A Gamal-Eldin, D. Macartney\",\"doi\":\"10.1155/2019/8124696\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<jats:p>The host-guest complexation of six amine boranes (R<jats:sub>3</jats:sub>NBH<jats:sub>3</jats:sub>) by the macrocyclic host molecule cucurbit<mml:math xmlns:mml=\\\"http://www.w3.org/1998/Math/MathML\\\" id=\\\"M1\\\"><mml:mo stretchy=\\\"false\\\">[</mml:mo><mml:mn fontstyle=\\\"italic\\\">7</mml:mn><mml:mo stretchy=\\\"false\\\">]</mml:mo></mml:math>uril (CB<mml:math xmlns:mml=\\\"http://www.w3.org/1998/Math/MathML\\\" id=\\\"M2\\\"><mml:mo stretchy=\\\"false\\\">[</mml:mo><mml:mn fontstyle=\\\"italic\\\">7</mml:mn><mml:mo stretchy=\\\"false\\\">]</mml:mo></mml:math>) in aqueous solution has been investigated using <jats:sup>1</jats:sup>H and <jats:sup>11</jats:sup>B NMR spectroscopy. The limiting complexation-induced <jats:sup>1</jats:sup>H and <jats:sup>11</jats:sup>B chemical shift changes indicate that the amine boranes are included in the hydrophobic cavity of the host molecule. The host-guest stability constants for neutral <mml:math xmlns:mml=\\\"http://www.w3.org/1998/Math/MathML\\\" id=\\\"M3\\\"><mml:mrow><mml:mfenced open=\\\"{\\\" close=\\\"\\\" separators=\\\"|\\\"><mml:mrow><mml:mo> </mml:mo></mml:mrow></mml:mfenced></mml:mrow></mml:math>R<jats:sub>3</jats:sub>NBH<jats:sub>3</jats:sub><jats:italic>∙</jats:italic>CB<mml:math xmlns:mml=\\\"http://www.w3.org/1998/Math/MathML\\\" id=\\\"M4\\\"><mml:mo stretchy=\\\"false\\\">[</mml:mo><mml:mn fontstyle=\\\"italic\\\">7</mml:mn><mml:mo stretchy=\\\"false\\\">]</mml:mo><mml:mfenced open=\\\"\\\" close=\\\"}\\\" separators=\\\"|\\\"><mml:mrow><mml:mo> </mml:mo></mml:mrow></mml:mfenced></mml:math> complexes (in the range of 10<jats:sup>5</jats:sup>-10<jats:sup>7</jats:sup><mml:math xmlns:mml=\\\"http://www.w3.org/1998/Math/MathML\\\" id=\\\"M5\\\"><mml:mrow><mml:msup><mml:mrow><mml:mi mathvariant=\\\"normal\\\">M</mml:mi></mml:mrow><mml:mrow><mml:mtext>-</mml:mtext><mml:mn mathvariant=\\\"normal\\\">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math>) have been determined by <jats:sup>1</jats:sup>H NMR competition experiments and are compared with the corresponding values for the isoelectronic/isostructural <mml:math xmlns:mml=\\\"http://www.w3.org/1998/Math/MathML\\\" id=\\\"M6\\\"><mml:mrow><mml:mfenced open=\\\"{\\\" close=\\\"\\\" separators=\\\"|\\\"><mml:mrow><mml:mo> </mml:mo></mml:mrow></mml:mfenced></mml:mrow></mml:math>R<jats:sub>3</jats:sub>NCH<jats:sub>3</jats:sub><jats:italic>∙</jats:italic>CB<mml:math xmlns:mml=\\\"http://www.w3.org/1998/Math/MathML\\\" id=\\\"M7\\\"><mml:mo stretchy=\\\"false\\\">[</mml:mo><mml:mn fontstyle=\\\"italic\\\">7</mml:mn><mml:mo stretchy=\\\"false\\\">]</mml:mo><mml:msup><mml:mrow><mml:mfenced open=\\\"\\\" close=\\\"}\\\" separators=\\\"|\\\"><mml:mrow><mml:mo> </mml:mo></mml:mrow></mml:mfenced></mml:mrow><mml:mrow><mml:mo>+</mml:mo></mml:mrow></mml:msup></mml:math> complexes. Ammonia borane (H<jats:sub>3</jats:sub>NBH<jats:sub>3</jats:sub>) does not form a host-guest complex with CB<mml:math xmlns:mml=\\\"http://www.w3.org/1998/Math/MathML\\\" id=\\\"M8\\\"><mml:mo stretchy=\\\"false\\\">[</mml:mo><mml:mn fontstyle=\\\"italic\\\">7</mml:mn><mml:mo stretchy=\\\"false\\\">]</mml:mo></mml:math>. The trends in the host-guest stability constant with the guest molar volume are examined, and the stability is ascribed to the hydrophobic effect (packing coefficient) and quadrupole-dipole interactions.</jats:p>\",\"PeriodicalId\":12816,\"journal\":{\"name\":\"Heteroatom Chemistry\",\"volume\":\" \",\"pages\":\"\"},\"PeriodicalIF\":1.1000,\"publicationDate\":\"2019-04-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1155/2019/8124696\",\"citationCount\":\"4\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Heteroatom Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1155/2019/8124696\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Heteroatom Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1155/2019/8124696","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Host-Guest Complexations of Amine Boranes and Isoelectronic/Isostructural Quaternary Alkylammonium Cations by Cucurbit[7]uril in Aqueous Solution
The host-guest complexation of six amine boranes (R3NBH3) by the macrocyclic host molecule cucurbit[7]uril (CB[7]) in aqueous solution has been investigated using 1H and 11B NMR spectroscopy. The limiting complexation-induced 1H and 11B chemical shift changes indicate that the amine boranes are included in the hydrophobic cavity of the host molecule. The host-guest stability constants for neutral R3NBH3∙CB[7] complexes (in the range of 105-107M-1) have been determined by 1H NMR competition experiments and are compared with the corresponding values for the isoelectronic/isostructural R3NCH3∙CB[7]+ complexes. Ammonia borane (H3NBH3) does not form a host-guest complex with CB[7]. The trends in the host-guest stability constant with the guest molar volume are examined, and the stability is ascribed to the hydrophobic effect (packing coefficient) and quadrupole-dipole interactions.
期刊介绍：
Heteroatom Chemistry brings together a broad, interdisciplinary group of chemists who work with compounds containing main-group elements of groups 13 through 17 of the Periodic Table, and certain other related elements. The fundamental reactivity under investigation should, in all cases, be concentrated about the heteroatoms. It does not matter whether the compounds being studied are acyclic or cyclic; saturated or unsaturated; monomeric, polymeric or solid state in nature; inorganic, organic, or naturally occurring, so long as the heteroatom is playing an essential role. Computational, experimental, and combined studies are equally welcome.
Subject areas include (but are by no means limited to):
-Reactivity about heteroatoms for accessing new products or synthetic pathways
-Unusual valency main-group element compounds and their properties
-Highly strained (e.g. bridged) main-group element compounds and their properties
-Photochemical or thermal cleavage of heteroatom bonds and the resulting reactivity
-Uncommon and structurally interesting heteroatom-containing species (including those containing multiple bonds and catenation)
-Stereochemistry of compounds due to the presence of heteroatoms
-Neighboring group effects of heteroatoms on the properties of compounds
-Main-group element compounds as analogues of transition metal compounds
-Variations and new results from established and named reactions (including Wittig, Kabachnik–Fields, Pudovik, Arbuzov, Hirao, and Mitsunobu)
-Catalysis and green syntheses enabled by heteroatoms and their chemistry
-Applications of compounds where the heteroatom plays a critical role.
In addition to original research articles on heteroatom chemistry, the journal welcomes focused review articles that examine the state of the art, identify emerging trends, and suggest future directions for developing fields.
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