دورية أكاديمية
Molecular structure of the solvated proton in isolated salts. Short, strong, low barrier (SSLB) H-bonds.
| العنوان: | Molecular structure of the solvated proton in isolated salts. Short, strong, low barrier (SSLB) H-bonds. |
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| المؤلفون: | Stasko D; Department of Chemistry, University of California, Riverside, California 92521-0403, USA., Hoffmann SP, Kim KC, Fackler NL, Larsen AS, Drovetskaya T, Tham FS, Reed CA, Rickard CE, Boyd PD, Stoyanov ES |
| المصدر: | Journal of the American Chemical Society [J Am Chem Soc] 2002 Nov 20; Vol. 124 (46), pp. 13869-76. |
| نوع المنشور: | Journal Article; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, Non-P.H.S.; Research Support, U.S. Gov't, P.H.S. |
| اللغة: | English |
| بيانات الدورية: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 7503056 Publication Model: Print Cited Medium: Print ISSN: 0002-7863 (Print) Linking ISSN: 00027863 NLM ISO Abbreviation: J Am Chem Soc Subsets: MEDLINE |
| أسماء مطبوعة: | Publication: Washington, DC : American Chemical Society Original Publication: Easton, Pa. [etc.] |
| مواضيع طبية MeSH: | Protons*, Benzophenones/*chemistry , Ethers/*chemistry , Nitrobenzenes/*chemistry, Anions ; Hydrogen Bonding ; Models, Molecular ; Spectrophotometry, Infrared |
| مستخلص: | Large, inert, weakly basic carborane anions of the icosahedral type CHB(11)R(5)X(6)(-) (R = H, Me; X = Cl, Br) allow ready isolation and structural characterization of discrete salts of the solvated proton, [H(solvent)(x)][CHB(11)R(5)X(6)], (solvent = common O-atom donor). These oxonium ion Brønsted acids are convenient reagents for the tuned delivery of protons to organic solvents with a specified number of donor solvent molecules and with acidities leveled to those of the chosen donor solvent. They have greater thermal stability than the popular [H(OEt(2))(2)][BAr(F)] acids based on fluorinated tetraphenylborate counterions because carborane anions can sustain much higher levels of acidity. When organic O-atom donors such as diethyl ether, tetrahydrofuran, benzophenone, and nitrobenzene are involved, the coordination number of the proton (x) in [H(solvent)(x)()](+) is two. A mixed species involving the [H(H(2)O)(diethyl ether)](+) ion has also been isolated. These solid-state structures provide expectations for the predominant molecular structures of solvated protons in solution and take into account that water is an inevitable impurity in organic solvents. The O.O distances are all short, lying within the range from 2.35 to 2.48 A. They are consistent with strong, linear O.H.O hydrogen bonding. Density functional theory calculations indicate that all H(solvent)(2)(+) cations have low barriers to movement of the proton within an interval along the O.H.O trajectory, i.e., they are examples of so-called SSLB H-bonds (short, strong, low-barrier). Unusually broadened IR bands, diagnostic of SSLB H-bonds, are observed in these H(solvent)(2)(+) cations. |
| معلومات مُعتمدة: | GM 23851 United States GM NIGMS NIH HHS |
| المشرفين على المادة: | 0 (Anions) 0 (Benzophenones) 0 (Ethers) 0 (Nitrobenzenes) 0 (Protons) 701M4TTV9O (benzophenone) E57JCN6SSY (nitrobenzene) |
| تواريخ الأحداث: | Date Created: 20021115 Date Completed: 20030130 Latest Revision: 20190708 |
| رمز التحديث: | 20240627 |
| DOI: | 10.1021/ja012671i |
| PMID: | 12431118 |
| قاعدة البيانات: | MEDLINE |
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