Transition state characterization for the hydrogen elimination from 1,4-cyclohexadiene
The gas phase thermal decomposition of various isotopically substituted 1,4-cyclohexadienes was studied in the 275-375/sup 0/C temperature region to obtain transition state information for the Woodward-Hoffman symmetry allowed hydrogen elimination reaction. Competitive decompositions with (i) a 1:1...
Gespeichert in:
| Veröffentlicht in: | J. Phys. Chem.; (United States) 1976-06, Vol.80 (13), p.1398-1400 |
|---|---|
| Hauptverfasser: | , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 1400 |
|---|---|
| container_issue | 13 |
| container_start_page | 1398 |
| container_title | J. Phys. Chem.; (United States) |
| container_volume | 80 |
| creator | Tardy, D. C Gordon, A. S Norris, W. P |
| description | The gas phase thermal decomposition of various isotopically substituted 1,4-cyclohexadienes was studied in the 275-375/sup 0/C temperature region to obtain transition state information for the Woodward-Hoffman symmetry allowed hydrogen elimination reaction. Competitive decompositions with (i) a 1:1 mix of 1,4-cyclohexadiene and perdeuterio-1,4-cyclohexadiene or (ii) 1,2,3,4,5,6-hexadeuterio-1,4-cyclohexadiene produced (1) H/sub 2/ and D/sub 2/ or (2) H/sub 2/, D/sub 2/, and HD. The difference in E/sub a/ for H/sub 2/ and D/sub 2/ elimination was 2.1 +- 0.4 and 2.4 +- 0.8 kcal/mol for systems (i) and (ii), respectively; the difference in E/sub a/ for H/sub 2/ and HD was 1.5 +- 0.4 kcal/mol. The results indicate a tight transition state which resembles benzene in its vibrational frequency assignment while the reaction coordinate is predominately the concerted breaking of two carbon-hydrogen bonds. |
| doi_str_mv | 10.1021/j100554a002 |
| format | Article |
| fullrecord | <record><control><sourceid>istex_osti_</sourceid><recordid>TN_cdi_crossref_primary_10_1021_j100554a002</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>ark_67375_TPS_292SC6T6_7</sourcerecordid><originalsourceid>FETCH-LOGICAL-a328t-b9852941e3f1f2573e0902234586a5d1588570f77bdd8db2bb61a8b849a3bfeb3</originalsourceid><addsrcrecordid>eNptkEtLxDAUhYMoOI6u_APFjQut5tmkSxl8gaAw1W1I0tRmnEkkiTDjr7faQVy4unDux7n3HACOEbxAEKPLBYKQMaogxDtgghhFJeMU7oLJoOCSVIzug4OUFhBCRAiagJcmKp9cdsEXKatsC9OrqEy20X2qH7kLsci9LfpNG8Or9YVdupXz22UMqwKd09JszDL0dq1aZ709BHudWiZ7tJ1T8Hxz3czuyofH2_vZ1UOpCBa51LVguKbIkg51mHFiYT08SigTlWItYkIwDjvOdduKVmOtK6SEFrRWRHdWkyk4GX1Dyk4m47I1vQneW5MlJ3QICQfobIRMDClF28n36FYqbiSC8rs3-ae3gS5H2qVs17-oim-y4oQz2TzNJa7xfFY11XBjCk5HXpkkF-Ej-iHwv85foKZ6zQ</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Transition state characterization for the hydrogen elimination from 1,4-cyclohexadiene</title><source>ACS Publications</source><creator>Tardy, D. C ; Gordon, A. S ; Norris, W. P</creator><creatorcontrib>Tardy, D. C ; Gordon, A. S ; Norris, W. P ; Naval Weapons Center, China Lake, CA</creatorcontrib><description>The gas phase thermal decomposition of various isotopically substituted 1,4-cyclohexadienes was studied in the 275-375/sup 0/C temperature region to obtain transition state information for the Woodward-Hoffman symmetry allowed hydrogen elimination reaction. Competitive decompositions with (i) a 1:1 mix of 1,4-cyclohexadiene and perdeuterio-1,4-cyclohexadiene or (ii) 1,2,3,4,5,6-hexadeuterio-1,4-cyclohexadiene produced (1) H/sub 2/ and D/sub 2/ or (2) H/sub 2/, D/sub 2/, and HD. The difference in E/sub a/ for H/sub 2/ and D/sub 2/ elimination was 2.1 +- 0.4 and 2.4 +- 0.8 kcal/mol for systems (i) and (ii), respectively; the difference in E/sub a/ for H/sub 2/ and HD was 1.5 +- 0.4 kcal/mol. The results indicate a tight transition state which resembles benzene in its vibrational frequency assignment while the reaction coordinate is predominately the concerted breaking of two carbon-hydrogen bonds.</description><identifier>ISSN: 0022-3654</identifier><identifier>EISSN: 1541-5740</identifier><identifier>DOI: 10.1021/j100554a002</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>400202 - Isotope Effects, Isotope Exchange, & Isotope Separation ; ALKANES ; CHEMICAL BONDS ; CHEMICAL REACTIONS ; CYCLOALKANES ; CYCLOHEXANE ; DECOMPOSITION ; DEUTERIUM ; DIENES ; HYDROCARBONS ; HYDROGEN ISOTOPES ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; ISOTOPE EFFECTS ; ISOTOPES ; LIGHT NUCLEI ; NUCLEI ; ODD-ODD NUCLEI ; ORGANIC COMPOUNDS ; POLYENES ; PYROLYSIS ; STABLE ISOTOPES</subject><ispartof>J. Phys. Chem.; (United States), 1976-06, Vol.80 (13), p.1398-1400</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a328t-b9852941e3f1f2573e0902234586a5d1588570f77bdd8db2bb61a8b849a3bfeb3</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/j100554a002$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/j100554a002$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>315,781,785,886,2766,27078,27926,27927,56740,56790</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/7341330$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Tardy, D. C</creatorcontrib><creatorcontrib>Gordon, A. S</creatorcontrib><creatorcontrib>Norris, W. P</creatorcontrib><creatorcontrib>Naval Weapons Center, China Lake, CA</creatorcontrib><title>Transition state characterization for the hydrogen elimination from 1,4-cyclohexadiene</title><title>J. Phys. Chem.; (United States)</title><addtitle>J. Phys. Chem</addtitle><description>The gas phase thermal decomposition of various isotopically substituted 1,4-cyclohexadienes was studied in the 275-375/sup 0/C temperature region to obtain transition state information for the Woodward-Hoffman symmetry allowed hydrogen elimination reaction. Competitive decompositions with (i) a 1:1 mix of 1,4-cyclohexadiene and perdeuterio-1,4-cyclohexadiene or (ii) 1,2,3,4,5,6-hexadeuterio-1,4-cyclohexadiene produced (1) H/sub 2/ and D/sub 2/ or (2) H/sub 2/, D/sub 2/, and HD. The difference in E/sub a/ for H/sub 2/ and D/sub 2/ elimination was 2.1 +- 0.4 and 2.4 +- 0.8 kcal/mol for systems (i) and (ii), respectively; the difference in E/sub a/ for H/sub 2/ and HD was 1.5 +- 0.4 kcal/mol. The results indicate a tight transition state which resembles benzene in its vibrational frequency assignment while the reaction coordinate is predominately the concerted breaking of two carbon-hydrogen bonds.</description><subject>400202 - Isotope Effects, Isotope Exchange, & Isotope Separation</subject><subject>ALKANES</subject><subject>CHEMICAL BONDS</subject><subject>CHEMICAL REACTIONS</subject><subject>CYCLOALKANES</subject><subject>CYCLOHEXANE</subject><subject>DECOMPOSITION</subject><subject>DEUTERIUM</subject><subject>DIENES</subject><subject>HYDROCARBONS</subject><subject>HYDROGEN ISOTOPES</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>ISOTOPE EFFECTS</subject><subject>ISOTOPES</subject><subject>LIGHT NUCLEI</subject><subject>NUCLEI</subject><subject>ODD-ODD NUCLEI</subject><subject>ORGANIC COMPOUNDS</subject><subject>POLYENES</subject><subject>PYROLYSIS</subject><subject>STABLE ISOTOPES</subject><issn>0022-3654</issn><issn>1541-5740</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1976</creationdate><recordtype>article</recordtype><recordid>eNptkEtLxDAUhYMoOI6u_APFjQut5tmkSxl8gaAw1W1I0tRmnEkkiTDjr7faQVy4unDux7n3HACOEbxAEKPLBYKQMaogxDtgghhFJeMU7oLJoOCSVIzug4OUFhBCRAiagJcmKp9cdsEXKatsC9OrqEy20X2qH7kLsci9LfpNG8Or9YVdupXz22UMqwKd09JszDL0dq1aZ709BHudWiZ7tJ1T8Hxz3czuyofH2_vZ1UOpCBa51LVguKbIkg51mHFiYT08SigTlWItYkIwDjvOdduKVmOtK6SEFrRWRHdWkyk4GX1Dyk4m47I1vQneW5MlJ3QICQfobIRMDClF28n36FYqbiSC8rs3-ae3gS5H2qVs17-oim-y4oQz2TzNJa7xfFY11XBjCk5HXpkkF-Ej-iHwv85foKZ6zQ</recordid><startdate>19760601</startdate><enddate>19760601</enddate><creator>Tardy, D. C</creator><creator>Gordon, A. S</creator><creator>Norris, W. P</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19760601</creationdate><title>Transition state characterization for the hydrogen elimination from 1,4-cyclohexadiene</title><author>Tardy, D. C ; Gordon, A. S ; Norris, W. P</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a328t-b9852941e3f1f2573e0902234586a5d1588570f77bdd8db2bb61a8b849a3bfeb3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1976</creationdate><topic>400202 - Isotope Effects, Isotope Exchange, & Isotope Separation</topic><topic>ALKANES</topic><topic>CHEMICAL BONDS</topic><topic>CHEMICAL REACTIONS</topic><topic>CYCLOALKANES</topic><topic>CYCLOHEXANE</topic><topic>DECOMPOSITION</topic><topic>DEUTERIUM</topic><topic>DIENES</topic><topic>HYDROCARBONS</topic><topic>HYDROGEN ISOTOPES</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>ISOTOPE EFFECTS</topic><topic>ISOTOPES</topic><topic>LIGHT NUCLEI</topic><topic>NUCLEI</topic><topic>ODD-ODD NUCLEI</topic><topic>ORGANIC COMPOUNDS</topic><topic>POLYENES</topic><topic>PYROLYSIS</topic><topic>STABLE ISOTOPES</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Tardy, D. C</creatorcontrib><creatorcontrib>Gordon, A. S</creatorcontrib><creatorcontrib>Norris, W. P</creatorcontrib><creatorcontrib>Naval Weapons Center, China Lake, CA</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Phys. Chem.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Tardy, D. C</au><au>Gordon, A. S</au><au>Norris, W. P</au><aucorp>Naval Weapons Center, China Lake, CA</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Transition state characterization for the hydrogen elimination from 1,4-cyclohexadiene</atitle><jtitle>J. Phys. Chem.; (United States)</jtitle><addtitle>J. Phys. Chem</addtitle><date>1976-06-01</date><risdate>1976</risdate><volume>80</volume><issue>13</issue><spage>1398</spage><epage>1400</epage><pages>1398-1400</pages><issn>0022-3654</issn><eissn>1541-5740</eissn><abstract>The gas phase thermal decomposition of various isotopically substituted 1,4-cyclohexadienes was studied in the 275-375/sup 0/C temperature region to obtain transition state information for the Woodward-Hoffman symmetry allowed hydrogen elimination reaction. Competitive decompositions with (i) a 1:1 mix of 1,4-cyclohexadiene and perdeuterio-1,4-cyclohexadiene or (ii) 1,2,3,4,5,6-hexadeuterio-1,4-cyclohexadiene produced (1) H/sub 2/ and D/sub 2/ or (2) H/sub 2/, D/sub 2/, and HD. The difference in E/sub a/ for H/sub 2/ and D/sub 2/ elimination was 2.1 +- 0.4 and 2.4 +- 0.8 kcal/mol for systems (i) and (ii), respectively; the difference in E/sub a/ for H/sub 2/ and HD was 1.5 +- 0.4 kcal/mol. The results indicate a tight transition state which resembles benzene in its vibrational frequency assignment while the reaction coordinate is predominately the concerted breaking of two carbon-hydrogen bonds.</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/j100554a002</doi><tpages>3</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0022-3654 |
| ispartof | J. Phys. Chem.; (United States), 1976-06, Vol.80 (13), p.1398-1400 |
| issn | 0022-3654 1541-5740 |
| language | eng |
| recordid | cdi_crossref_primary_10_1021_j100554a002 |
| source | ACS Publications |
| subjects | 400202 - Isotope Effects, Isotope Exchange, & Isotope Separation ALKANES CHEMICAL BONDS CHEMICAL REACTIONS CYCLOALKANES CYCLOHEXANE DECOMPOSITION DEUTERIUM DIENES HYDROCARBONS HYDROGEN ISOTOPES INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ISOTOPE EFFECTS ISOTOPES LIGHT NUCLEI NUCLEI ODD-ODD NUCLEI ORGANIC COMPOUNDS POLYENES PYROLYSIS STABLE ISOTOPES |
| title | Transition state characterization for the hydrogen elimination from 1,4-cyclohexadiene |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-18T07%3A35%3A15IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-istex_osti_&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Transition%20state%20characterization%20for%20the%20hydrogen%20elimination%20from%201,4-cyclohexadiene&rft.jtitle=J.%20Phys.%20Chem.;%20(United%20States)&rft.au=Tardy,%20D.%20C&rft.aucorp=Naval%20Weapons%20Center,%20China%20Lake,%20CA&rft.date=1976-06-01&rft.volume=80&rft.issue=13&rft.spage=1398&rft.epage=1400&rft.pages=1398-1400&rft.issn=0022-3654&rft.eissn=1541-5740&rft_id=info:doi/10.1021/j100554a002&rft_dat=%3Cistex_osti_%3Eark_67375_TPS_292SC6T6_7%3C/istex_osti_%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true |