The use of chlorine kinetic isotope effects for evaluating ion pairing in nucleophilic displacements at saturated carbon
Use of the Winstein scheme to describe ion pairing leads to the conclusion that chlorine kinetic isotope effects (KIE) are primarily responsive to processes involving the covalently bound chlorine and less indicative of reactions which occur after the formation of the initial ion pair. This conclusi...
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| Veröffentlicht in: | J. Am. Chem. Soc.; (United States) 1978-11, Vol.100 (23), p.7333-7339 |
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| creator | Graczyk, Donald G Taylor, James W Turnquist, Carl R |
| description | Use of the Winstein scheme to describe ion pairing leads to the conclusion that chlorine kinetic isotope effects (KIE) are primarily responsive to processes involving the covalently bound chlorine and less indicative of reactions which occur after the formation of the initial ion pair. This conclusion has been tested by showing that the calculated equilibrium isotope effect (1.0057) and observed (1.0059/sub 6/ +- 0.0001/sub 1/) KIE are nearly identical when the solvolysis of p-methylbenzyl chloride is forced toward a limiting case with 97% trifluoroethanol as solvent. The reaction of p-phenoxybenzyl chloride showed similar behavior with an equilibrium KIE value of 1.0058/sub 4/ +- 0.0001/sub 1/. These results suggest that competing ion-pair and S/sub N/2 processes may be one factor contributing to Hammett plot curvature for these nucleophilic displacement reactions. Chloride KIE values for the reaction of n-butyl chloride with thiophenoxide anion, where ion pairing does not occur, show little variation with a wide variety of solvents. 3 tables. |
| doi_str_mv | 10.1021/ja00491a034 |
| format | Article |
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This conclusion has been tested by showing that the calculated equilibrium isotope effect (1.0057) and observed (1.0059/sub 6/ +- 0.0001/sub 1/) KIE are nearly identical when the solvolysis of p-methylbenzyl chloride is forced toward a limiting case with 97% trifluoroethanol as solvent. The reaction of p-phenoxybenzyl chloride showed similar behavior with an equilibrium KIE value of 1.0058/sub 4/ +- 0.0001/sub 1/. These results suggest that competing ion-pair and S/sub N/2 processes may be one factor contributing to Hammett plot curvature for these nucleophilic displacement reactions. Chloride KIE values for the reaction of n-butyl chloride with thiophenoxide anion, where ion pairing does not occur, show little variation with a wide variety of solvents. 3 tables.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja00491a034</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987) ; 400302 - Organic Chemistry- Isotope Effects- (-1987) ; AROMATICS ; CHEMICAL REACTION KINETICS ; CHEMICAL REACTION YIELD ; CHEMICAL REACTIONS ; CHLORINATED ALIPHATIC HYDROCARBONS ; CHLORINATED AROMATIC HYDROCARBONS ; CHLORINE 37 ; CHLORINE ISOTOPES ; DECOMPOSITION ; ENERGY LEVELS ; EQUILIBRIUM ; GROUND STATES ; HALOGENATED ALIPHATIC HYDROCARBONS ; HALOGENATED AROMATIC HYDROCARBONS ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; ION PAIRS ; ISOTOPE EFFECTS ; ISOTOPES ; KINETICS ; LIGHT NUCLEI ; MEDIUM TEMPERATURE ; NUCLEI ; ODD-EVEN NUCLEI ; ORGANIC CHLORINE COMPOUNDS ; ORGANIC COMPOUNDS ; ORGANIC FLUORINE COMPOUNDS ; ORGANIC HALOGEN COMPOUNDS ; ORGANIC SOLVENTS ; ORGANIC SULFUR COMPOUNDS ; REACTION KINETICS ; SOLVENTS ; SOLVOLYSIS ; STABLE ISOTOPES ; TEMPERATURE DEPENDENCE ; YIELDS</subject><ispartof>J. Am. Chem. Soc.; (United States), 1978-11, Vol.100 (23), p.7333-7339</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a328t-f125dc9afc93d1fbbd9bc35868f70e536703992e5bb7cc938e78b924c7cca9293</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja00491a034$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja00491a034$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,885,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/6389618$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Graczyk, Donald G</creatorcontrib><creatorcontrib>Taylor, James W</creatorcontrib><creatorcontrib>Turnquist, Carl R</creatorcontrib><creatorcontrib>Univ. of Wisconsin, Madison</creatorcontrib><title>The use of chlorine kinetic isotope effects for evaluating ion pairing in nucleophilic displacements at saturated carbon</title><title>J. Am. Chem. Soc.; (United States)</title><addtitle>J. Am. Chem. Soc</addtitle><description>Use of the Winstein scheme to describe ion pairing leads to the conclusion that chlorine kinetic isotope effects (KIE) are primarily responsive to processes involving the covalently bound chlorine and less indicative of reactions which occur after the formation of the initial ion pair. This conclusion has been tested by showing that the calculated equilibrium isotope effect (1.0057) and observed (1.0059/sub 6/ +- 0.0001/sub 1/) KIE are nearly identical when the solvolysis of p-methylbenzyl chloride is forced toward a limiting case with 97% trifluoroethanol as solvent. The reaction of p-phenoxybenzyl chloride showed similar behavior with an equilibrium KIE value of 1.0058/sub 4/ +- 0.0001/sub 1/. These results suggest that competing ion-pair and S/sub N/2 processes may be one factor contributing to Hammett plot curvature for these nucleophilic displacement reactions. Chloride KIE values for the reaction of n-butyl chloride with thiophenoxide anion, where ion pairing does not occur, show little variation with a wide variety of solvents. 3 tables.</description><subject>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)</subject><subject>400302 - Organic Chemistry- Isotope Effects- (-1987)</subject><subject>AROMATICS</subject><subject>CHEMICAL REACTION KINETICS</subject><subject>CHEMICAL REACTION YIELD</subject><subject>CHEMICAL REACTIONS</subject><subject>CHLORINATED ALIPHATIC HYDROCARBONS</subject><subject>CHLORINATED AROMATIC HYDROCARBONS</subject><subject>CHLORINE 37</subject><subject>CHLORINE ISOTOPES</subject><subject>DECOMPOSITION</subject><subject>ENERGY LEVELS</subject><subject>EQUILIBRIUM</subject><subject>GROUND STATES</subject><subject>HALOGENATED ALIPHATIC HYDROCARBONS</subject><subject>HALOGENATED AROMATIC HYDROCARBONS</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>ION PAIRS</subject><subject>ISOTOPE EFFECTS</subject><subject>ISOTOPES</subject><subject>KINETICS</subject><subject>LIGHT NUCLEI</subject><subject>MEDIUM TEMPERATURE</subject><subject>NUCLEI</subject><subject>ODD-EVEN NUCLEI</subject><subject>ORGANIC CHLORINE COMPOUNDS</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANIC FLUORINE COMPOUNDS</subject><subject>ORGANIC HALOGEN COMPOUNDS</subject><subject>ORGANIC SOLVENTS</subject><subject>ORGANIC SULFUR COMPOUNDS</subject><subject>REACTION KINETICS</subject><subject>SOLVENTS</subject><subject>SOLVOLYSIS</subject><subject>STABLE ISOTOPES</subject><subject>TEMPERATURE DEPENDENCE</subject><subject>YIELDS</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1978</creationdate><recordtype>article</recordtype><recordid>eNptkE-LFDEQxYMoOK6e_ALBiwfpNX-mO8lRh9UV1lVwvOwlVKcrTmZ7kyZJy_rtjY6IBy9V9eD3Hrwi5Dln55wJ_voIjG0NBya3D8iG94J1PRfDQ7JhjIlO6UE-Jk9KOTa5FZpvyP3-gHQtSJOn7jCnHCLS2zZqcDSUVNOCFL1HVwv1KVP8DvMKNcRvNKRIFwj59x1pXN2MaTmEuVmnUJYZHN5hbEaotEBdM1ScqIM8pviUPPIwF3z2Z5-Rr-8u9rvL7urT-w-7N1cdSKFr57noJ2fAOyMn7sdxMqOTvR60Vwx7OSgmjRHYj6NyjdGo9GjE1jUFRhh5Rl6cclOpwRYXKrqDSzG2RnaQ2gxcN-jVCXI5lZLR2yWHO8g_LGf212ftP59tdHeiQ6l4_xeFfGsHJVVv95-_WHWjPl6_vdnZ68a_PPHgij2mNcdW-L_JPwFyuomY</recordid><startdate>19781101</startdate><enddate>19781101</enddate><creator>Graczyk, Donald G</creator><creator>Taylor, James W</creator><creator>Turnquist, Carl R</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19781101</creationdate><title>The use of chlorine kinetic isotope effects for evaluating ion pairing in nucleophilic displacements at saturated carbon</title><author>Graczyk, Donald G ; Taylor, James W ; Turnquist, Carl R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a328t-f125dc9afc93d1fbbd9bc35868f70e536703992e5bb7cc938e78b924c7cca9293</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1978</creationdate><topic>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)</topic><topic>400302 - Organic Chemistry- Isotope Effects- (-1987)</topic><topic>AROMATICS</topic><topic>CHEMICAL REACTION KINETICS</topic><topic>CHEMICAL REACTION YIELD</topic><topic>CHEMICAL REACTIONS</topic><topic>CHLORINATED ALIPHATIC HYDROCARBONS</topic><topic>CHLORINATED AROMATIC HYDROCARBONS</topic><topic>CHLORINE 37</topic><topic>CHLORINE ISOTOPES</topic><topic>DECOMPOSITION</topic><topic>ENERGY LEVELS</topic><topic>EQUILIBRIUM</topic><topic>GROUND STATES</topic><topic>HALOGENATED ALIPHATIC HYDROCARBONS</topic><topic>HALOGENATED AROMATIC HYDROCARBONS</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>ION PAIRS</topic><topic>ISOTOPE EFFECTS</topic><topic>ISOTOPES</topic><topic>KINETICS</topic><topic>LIGHT NUCLEI</topic><topic>MEDIUM TEMPERATURE</topic><topic>NUCLEI</topic><topic>ODD-EVEN NUCLEI</topic><topic>ORGANIC CHLORINE COMPOUNDS</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANIC FLUORINE COMPOUNDS</topic><topic>ORGANIC HALOGEN COMPOUNDS</topic><topic>ORGANIC SOLVENTS</topic><topic>ORGANIC SULFUR COMPOUNDS</topic><topic>REACTION KINETICS</topic><topic>SOLVENTS</topic><topic>SOLVOLYSIS</topic><topic>STABLE ISOTOPES</topic><topic>TEMPERATURE DEPENDENCE</topic><topic>YIELDS</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Graczyk, Donald G</creatorcontrib><creatorcontrib>Taylor, James W</creatorcontrib><creatorcontrib>Turnquist, Carl R</creatorcontrib><creatorcontrib>Univ. of Wisconsin, Madison</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>Graczyk, Donald G</au><au>Taylor, James W</au><au>Turnquist, Carl R</au><aucorp>Univ. of Wisconsin, Madison</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The use of chlorine kinetic isotope effects for evaluating ion pairing in nucleophilic displacements at saturated carbon</atitle><jtitle>J. Am. Chem. Soc.; (United States)</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>1978-11-01</date><risdate>1978</risdate><volume>100</volume><issue>23</issue><spage>7333</spage><epage>7339</epage><pages>7333-7339</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Use of the Winstein scheme to describe ion pairing leads to the conclusion that chlorine kinetic isotope effects (KIE) are primarily responsive to processes involving the covalently bound chlorine and less indicative of reactions which occur after the formation of the initial ion pair. This conclusion has been tested by showing that the calculated equilibrium isotope effect (1.0057) and observed (1.0059/sub 6/ +- 0.0001/sub 1/) KIE are nearly identical when the solvolysis of p-methylbenzyl chloride is forced toward a limiting case with 97% trifluoroethanol as solvent. The reaction of p-phenoxybenzyl chloride showed similar behavior with an equilibrium KIE value of 1.0058/sub 4/ +- 0.0001/sub 1/. These results suggest that competing ion-pair and S/sub N/2 processes may be one factor contributing to Hammett plot curvature for these nucleophilic displacement reactions. Chloride KIE values for the reaction of n-butyl chloride with thiophenoxide anion, where ion pairing does not occur, show little variation with a wide variety of solvents. 3 tables.</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/ja00491a034</doi><tpages>7</tpages></addata></record> |
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| subjects | 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987) 400302 - Organic Chemistry- Isotope Effects- (-1987) AROMATICS CHEMICAL REACTION KINETICS CHEMICAL REACTION YIELD CHEMICAL REACTIONS CHLORINATED ALIPHATIC HYDROCARBONS CHLORINATED AROMATIC HYDROCARBONS CHLORINE 37 CHLORINE ISOTOPES DECOMPOSITION ENERGY LEVELS EQUILIBRIUM GROUND STATES HALOGENATED ALIPHATIC HYDROCARBONS HALOGENATED AROMATIC HYDROCARBONS INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ION PAIRS ISOTOPE EFFECTS ISOTOPES KINETICS LIGHT NUCLEI MEDIUM TEMPERATURE NUCLEI ODD-EVEN NUCLEI ORGANIC CHLORINE COMPOUNDS ORGANIC COMPOUNDS ORGANIC FLUORINE COMPOUNDS ORGANIC HALOGEN COMPOUNDS ORGANIC SOLVENTS ORGANIC SULFUR COMPOUNDS REACTION KINETICS SOLVENTS SOLVOLYSIS STABLE ISOTOPES TEMPERATURE DEPENDENCE YIELDS |
| title | The use of chlorine kinetic isotope effects for evaluating ion pairing in nucleophilic displacements at saturated carbon |
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