Carbon acidity. 71. The indicator scale of lithium ion pairs in tetrahydrofuran
An equilibrium lithium ion pair indicator scale has been established for eight hydrocarbons that form solvent-separated ion pairs in THF. The scale covers the pK/sub a/ range from 18.49 to 23.84 relative to 9-phenylfluorene at pK/sub a/ = 18.49. This range allows the study of enolates and other high...
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| Veröffentlicht in: | J. Am. Chem. Soc.; (United States) 1986-10, Vol.108 (22), p.7016-7022 |
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| container_issue | 22 |
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| container_title | J. Am. Chem. Soc.; (United States) |
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| creator | Gronert, Scott Streitwieser, Andrew |
| description | An equilibrium lithium ion pair indicator scale has been established for eight hydrocarbons that form solvent-separated ion pairs in THF. The scale covers the pK/sub a/ range from 18.49 to 23.84 relative to 9-phenylfluorene at pK/sub a/ = 18.49. This range allows the study of enolates and other highly stabilized anions under realistic synthetic reaction conditions. Equilibria were monitored with UV-vis spectroscopy, and the indicator anion spectra are reported. Thermodynamic measurements of the indicator equilibria yield small ..delta..S/sup 0/ values indicating that all of the solvent-separated ion pairs must have similar structures and solvation. Comparison of these thermodynamic parameters with those measured for the analogous cesium ion pairs points out the more complex nature of organocesium ion pairing. Aggregation studies indicate that the organolithium salts exist predominantly, if not exclusively, as monomers in the concentration range employed (10/sup -3/-10/sup -4/ M). |
| doi_str_mv | 10.1021/ja00282a028 |
| format | Article |
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The indicator scale of lithium ion pairs in tetrahydrofuran</title><source>ACS Publications</source><creator>Gronert, Scott ; Streitwieser, Andrew</creator><creatorcontrib>Gronert, Scott ; Streitwieser, Andrew ; Univ. of California, Berkeley</creatorcontrib><description>An equilibrium lithium ion pair indicator scale has been established for eight hydrocarbons that form solvent-separated ion pairs in THF. The scale covers the pK/sub a/ range from 18.49 to 23.84 relative to 9-phenylfluorene at pK/sub a/ = 18.49. This range allows the study of enolates and other highly stabilized anions under realistic synthetic reaction conditions. Equilibria were monitored with UV-vis spectroscopy, and the indicator anion spectra are reported. Thermodynamic measurements of the indicator equilibria yield small ..delta..S/sup 0/ values indicating that all of the solvent-separated ion pairs must have similar structures and solvation. Comparison of these thermodynamic parameters with those measured for the analogous cesium ion pairs points out the more complex nature of organocesium ion pairing. Aggregation studies indicate that the organolithium salts exist predominantly, if not exclusively, as monomers in the concentration range employed (10/sup -3/-10/sup -4/ M).</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja00282a028</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>400201 - Chemical & Physicochemical Properties ; ALKALI METAL COMPOUNDS ; ANIONS ; CESIUM COMPOUNDS ; CHARGED PARTICLES ; DATA ; EQUILIBRIUM ; EXPERIMENTAL DATA ; FURANS ; HETEROCYCLIC COMPOUNDS ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; IONS ; LITHIUM COMPOUNDS ; NUMERICAL DATA ; ORGANIC COMPOUNDS ; ORGANIC OXYGEN COMPOUNDS ; ORGANOMETALLIC COMPOUNDS ; PH VALUE ; PHYSICAL PROPERTIES ; SOLVATION ; SPECTRA ; TETRAHYDROFURAN ; THERMODYNAMIC PROPERTIES ; ULTRAVIOLET SPECTRA</subject><ispartof>J. Am. Chem. 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The indicator scale of lithium ion pairs in tetrahydrofuran</title><title>J. Am. Chem. Soc.; (United States)</title><addtitle>J. Am. Chem. Soc</addtitle><description>An equilibrium lithium ion pair indicator scale has been established for eight hydrocarbons that form solvent-separated ion pairs in THF. The scale covers the pK/sub a/ range from 18.49 to 23.84 relative to 9-phenylfluorene at pK/sub a/ = 18.49. This range allows the study of enolates and other highly stabilized anions under realistic synthetic reaction conditions. Equilibria were monitored with UV-vis spectroscopy, and the indicator anion spectra are reported. Thermodynamic measurements of the indicator equilibria yield small ..delta..S/sup 0/ values indicating that all of the solvent-separated ion pairs must have similar structures and solvation. Comparison of these thermodynamic parameters with those measured for the analogous cesium ion pairs points out the more complex nature of organocesium ion pairing. Aggregation studies indicate that the organolithium salts exist predominantly, if not exclusively, as monomers in the concentration range employed (10/sup -3/-10/sup -4/ M).</description><subject>400201 - Chemical & Physicochemical Properties</subject><subject>ALKALI METAL COMPOUNDS</subject><subject>ANIONS</subject><subject>CESIUM COMPOUNDS</subject><subject>CHARGED PARTICLES</subject><subject>DATA</subject><subject>EQUILIBRIUM</subject><subject>EXPERIMENTAL DATA</subject><subject>FURANS</subject><subject>HETEROCYCLIC COMPOUNDS</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>IONS</subject><subject>LITHIUM COMPOUNDS</subject><subject>NUMERICAL DATA</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANIC OXYGEN COMPOUNDS</subject><subject>ORGANOMETALLIC COMPOUNDS</subject><subject>PH VALUE</subject><subject>PHYSICAL PROPERTIES</subject><subject>SOLVATION</subject><subject>SPECTRA</subject><subject>TETRAHYDROFURAN</subject><subject>THERMODYNAMIC PROPERTIES</subject><subject>ULTRAVIOLET SPECTRA</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1986</creationdate><recordtype>article</recordtype><recordid>eNpt0F9LwzAQAPAgCs7pk18g-OKDdOZP26SPWpyKwwlO8C3ckpRmbu1IMnDf3khFfBCOO477cXCH0DklE0oYvV4BIUwySOkAjWjBSFZQVh6iEUmDTMiSH6OTEFapzZmkIzSvwS_7DoN2xsX9BAs6wYvWYtcZpyH2HgcNa4v7Bq9dbN1ug13yW3A-JISjjR7avfF9s_PQnaKjBtbBnv3UMXqb3i3qh2w2v3-sb2YZcCZjJqulLkgKYQwUFoCXS05yCZQVkFe5YFwTRkQyVVmCLo2VxnDJpbSMasHH6GLY24foVNAuWt3qvuusjkowwkshE7oakPZ9CN42auvdBvxeUaK-H6b-PCzpbNAuRPv5S8F_qFJwUajFy6uqnqb0-bam6j35y8GDDmrV73yXDv538xdDOXeX</recordid><startdate>19861001</startdate><enddate>19861001</enddate><creator>Gronert, Scott</creator><creator>Streitwieser, Andrew</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19861001</creationdate><title>Carbon acidity. 71. The indicator scale of lithium ion pairs in tetrahydrofuran</title><author>Gronert, Scott ; Streitwieser, Andrew</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a328t-89bc50c507dda5eaa36b3048a125a494723c020750c966ac6de8dd38388e21c73</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1986</creationdate><topic>400201 - Chemical & Physicochemical Properties</topic><topic>ALKALI METAL COMPOUNDS</topic><topic>ANIONS</topic><topic>CESIUM COMPOUNDS</topic><topic>CHARGED PARTICLES</topic><topic>DATA</topic><topic>EQUILIBRIUM</topic><topic>EXPERIMENTAL DATA</topic><topic>FURANS</topic><topic>HETEROCYCLIC COMPOUNDS</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>IONS</topic><topic>LITHIUM COMPOUNDS</topic><topic>NUMERICAL DATA</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANIC OXYGEN COMPOUNDS</topic><topic>ORGANOMETALLIC COMPOUNDS</topic><topic>PH VALUE</topic><topic>PHYSICAL PROPERTIES</topic><topic>SOLVATION</topic><topic>SPECTRA</topic><topic>TETRAHYDROFURAN</topic><topic>THERMODYNAMIC PROPERTIES</topic><topic>ULTRAVIOLET SPECTRA</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Gronert, Scott</creatorcontrib><creatorcontrib>Streitwieser, Andrew</creatorcontrib><creatorcontrib>Univ. of California, Berkeley</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Am. Chem. Soc.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Gronert, Scott</au><au>Streitwieser, Andrew</au><aucorp>Univ. of California, Berkeley</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Carbon acidity. 71. The indicator scale of lithium ion pairs in tetrahydrofuran</atitle><jtitle>J. Am. Chem. Soc.; (United States)</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>1986-10-01</date><risdate>1986</risdate><volume>108</volume><issue>22</issue><spage>7016</spage><epage>7022</epage><pages>7016-7022</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>An equilibrium lithium ion pair indicator scale has been established for eight hydrocarbons that form solvent-separated ion pairs in THF. The scale covers the pK/sub a/ range from 18.49 to 23.84 relative to 9-phenylfluorene at pK/sub a/ = 18.49. This range allows the study of enolates and other highly stabilized anions under realistic synthetic reaction conditions. Equilibria were monitored with UV-vis spectroscopy, and the indicator anion spectra are reported. Thermodynamic measurements of the indicator equilibria yield small ..delta..S/sup 0/ values indicating that all of the solvent-separated ion pairs must have similar structures and solvation. Comparison of these thermodynamic parameters with those measured for the analogous cesium ion pairs points out the more complex nature of organocesium ion pairing. Aggregation studies indicate that the organolithium salts exist predominantly, if not exclusively, as monomers in the concentration range employed (10/sup -3/-10/sup -4/ M).</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/ja00282a028</doi><tpages>7</tpages></addata></record> |
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| identifier | ISSN: 0002-7863 |
| ispartof | J. Am. Chem. Soc.; (United States), 1986-10, Vol.108 (22), p.7016-7022 |
| issn | 0002-7863 1520-5126 |
| language | eng |
| recordid | cdi_crossref_primary_10_1021_ja00282a028 |
| source | ACS Publications |
| subjects | 400201 - Chemical & Physicochemical Properties ALKALI METAL COMPOUNDS ANIONS CESIUM COMPOUNDS CHARGED PARTICLES DATA EQUILIBRIUM EXPERIMENTAL DATA FURANS HETEROCYCLIC COMPOUNDS INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY IONS LITHIUM COMPOUNDS NUMERICAL DATA ORGANIC COMPOUNDS ORGANIC OXYGEN COMPOUNDS ORGANOMETALLIC COMPOUNDS PH VALUE PHYSICAL PROPERTIES SOLVATION SPECTRA TETRAHYDROFURAN THERMODYNAMIC PROPERTIES ULTRAVIOLET SPECTRA |
| title | Carbon acidity. 71. The indicator scale of lithium ion pairs in tetrahydrofuran |
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