Barriers to internal rotation around the C-N bond in 3-(o-aryl)-5-methyl-rhodanines using NMR spectroscopy and computational studies. Electron density topological analysis of the transition states
We have investigated the pairs of rotational isomers for six 3-(o-aryl)-5-methyl-rhodanines (Z = H, F, Cl, Br, OH, and CH3) using NMR spectroscopy and density functional theory (DFT) calculations. Electron density topological and NBO analysis has demonstrated the importance of non-covalent interacti...
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| Veröffentlicht in: | Organic & biomolecular chemistry 2004-09, Vol.2 (17), p.2426-2436 |
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| container_title | Organic & biomolecular chemistry |
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| creator | Aydeniz, Yeliz Oguz, Funda Yaman, Arzu Konuklar, Aylin Sungur Dogan, Ilknur Aviyente, Viktorya Klein, Roger A |
| description | We have investigated the pairs of rotational isomers for six 3-(o-aryl)-5-methyl-rhodanines (Z = H, F, Cl, Br, OH, and CH3) using NMR spectroscopy and density functional theory (DFT) calculations. Electron density topological and NBO analysis has demonstrated the importance of non-covalent interactions, characterised by (3, -1) bond critical points (BCPs), between the oxygen and sulfur atoms on the thiazolidine ring with the aryl substitutents in stabilizing the transition states. The energetic activation barriers to rotation have also been determined using computational results; rotational barriers for 3-(o-chlorophenyl)-5-methyl-rhodanine (3S) and 3-(o-tolyl)-5-methyl-rhodanine (6S) were determined experimentally based on NMR separation of the diastereoisomeric pairs, and the first-order rate constants used to derive the value of the rotational barrier from the Eyring equation. |
| doi_str_mv | 10.1039/B406556E |
| format | Article |
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Electron density topological analysis of the transition states</title><source>Royal Society of Chemistry Journals Archive (1841-2007)</source><source>MEDLINE</source><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Aydeniz, Yeliz ; Oguz, Funda ; Yaman, Arzu ; Konuklar, Aylin Sungur ; Dogan, Ilknur ; Aviyente, Viktorya ; Klein, Roger A</creator><creatorcontrib>Aydeniz, Yeliz ; Oguz, Funda ; Yaman, Arzu ; Konuklar, Aylin Sungur ; Dogan, Ilknur ; Aviyente, Viktorya ; Klein, Roger A</creatorcontrib><description>We have investigated the pairs of rotational isomers for six 3-(o-aryl)-5-methyl-rhodanines (Z = H, F, Cl, Br, OH, and CH3) using NMR spectroscopy and density functional theory (DFT) calculations. Electron density topological and NBO analysis has demonstrated the importance of non-covalent interactions, characterised by (3, -1) bond critical points (BCPs), between the oxygen and sulfur atoms on the thiazolidine ring with the aryl substitutents in stabilizing the transition states. The energetic activation barriers to rotation have also been determined using computational results; rotational barriers for 3-(o-chlorophenyl)-5-methyl-rhodanine (3S) and 3-(o-tolyl)-5-methyl-rhodanine (6S) were determined experimentally based on NMR separation of the diastereoisomeric pairs, and the first-order rate constants used to derive the value of the rotational barrier from the Eyring equation.</description><identifier>ISSN: 1477-0520</identifier><identifier>EISSN: 1477-0539</identifier><identifier>DOI: 10.1039/B406556E</identifier><identifier>PMID: 15326522</identifier><language>eng</language><publisher>England</publisher><subject>Computer Simulation ; Electrons ; Isomerism ; Magnetic Resonance Spectroscopy - methods ; Models, Chemical ; Molecular Conformation ; Rhodanine - analogs & derivatives ; Rhodanine - chemistry ; Rotation ; Thermodynamics</subject><ispartof>Organic & biomolecular chemistry, 2004-09, Vol.2 (17), p.2426-2436</ispartof><rights>Copyright 2004 The Royal Society of Chemistry</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c299t-12e2f98a9cca8cf0ebe001308eae2e9395e529023fdb23098c09e87ae56af1063</citedby><cites>FETCH-LOGICAL-c299t-12e2f98a9cca8cf0ebe001308eae2e9395e529023fdb23098c09e87ae56af1063</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,2818,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15326522$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Aydeniz, Yeliz</creatorcontrib><creatorcontrib>Oguz, Funda</creatorcontrib><creatorcontrib>Yaman, Arzu</creatorcontrib><creatorcontrib>Konuklar, Aylin Sungur</creatorcontrib><creatorcontrib>Dogan, Ilknur</creatorcontrib><creatorcontrib>Aviyente, Viktorya</creatorcontrib><creatorcontrib>Klein, Roger A</creatorcontrib><title>Barriers to internal rotation around the C-N bond in 3-(o-aryl)-5-methyl-rhodanines using NMR spectroscopy and computational studies. Electron density topological analysis of the transition states</title><title>Organic & biomolecular chemistry</title><addtitle>Org Biomol Chem</addtitle><description>We have investigated the pairs of rotational isomers for six 3-(o-aryl)-5-methyl-rhodanines (Z = H, F, Cl, Br, OH, and CH3) using NMR spectroscopy and density functional theory (DFT) calculations. Electron density topological and NBO analysis has demonstrated the importance of non-covalent interactions, characterised by (3, -1) bond critical points (BCPs), between the oxygen and sulfur atoms on the thiazolidine ring with the aryl substitutents in stabilizing the transition states. The energetic activation barriers to rotation have also been determined using computational results; rotational barriers for 3-(o-chlorophenyl)-5-methyl-rhodanine (3S) and 3-(o-tolyl)-5-methyl-rhodanine (6S) were determined experimentally based on NMR separation of the diastereoisomeric pairs, and the first-order rate constants used to derive the value of the rotational barrier from the Eyring equation.</description><subject>Computer Simulation</subject><subject>Electrons</subject><subject>Isomerism</subject><subject>Magnetic Resonance Spectroscopy - methods</subject><subject>Models, Chemical</subject><subject>Molecular Conformation</subject><subject>Rhodanine - analogs & derivatives</subject><subject>Rhodanine - chemistry</subject><subject>Rotation</subject><subject>Thermodynamics</subject><issn>1477-0520</issn><issn>1477-0539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2004</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpFkUtv1DAUhS1ERR8g8QuQV6gs3PoxTuIlHQ0FqQ8JwTryODcdo8QOvs4i_48fVk9ngNX1lT4fH59DyHvBrwRX5vpmxSutq80rciZWdc24Vub1v7Pkp-Qc8RfnwtTV6g05FVrJSkt5Rv7c2JQ8JKQ5Uh8ypGAHmmK22cdAbYpz6GjeAV2zB7qNZfGBKnYZmU3L8IlpNkLeLQNLu9jZ4AMgndGHJ_pw_53iBC6niC5OC7XlsovjNB_EyzuY584DXtHN8MIF2kFAn5fiZopDfPKuULagC3qksX9xkpPdQ3t_WKQA35KT3g4I747zgvz8svmx_sruHm-_rT_fMSeNyUxIkL1prHHONq7nsIUSieINWJBglNGgpeFS9d1WKm4axw00tQVd2V7wSl2QjwfdKcXfM2BuR48OhsEGiDO2VdUIblRdwMsD6MrfMUHfTsmPJbBW8HbfWPu3sYJ-OGrO2xG6_-CxIvUMsQWUzA</recordid><startdate>20040907</startdate><enddate>20040907</enddate><creator>Aydeniz, Yeliz</creator><creator>Oguz, Funda</creator><creator>Yaman, Arzu</creator><creator>Konuklar, Aylin Sungur</creator><creator>Dogan, Ilknur</creator><creator>Aviyente, Viktorya</creator><creator>Klein, Roger A</creator><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20040907</creationdate><title>Barriers to internal rotation around the C-N bond in 3-(o-aryl)-5-methyl-rhodanines using NMR spectroscopy and computational studies. Electron density topological analysis of the transition states</title><author>Aydeniz, Yeliz ; Oguz, Funda ; Yaman, Arzu ; Konuklar, Aylin Sungur ; Dogan, Ilknur ; Aviyente, Viktorya ; Klein, Roger A</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c299t-12e2f98a9cca8cf0ebe001308eae2e9395e529023fdb23098c09e87ae56af1063</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2004</creationdate><topic>Computer Simulation</topic><topic>Electrons</topic><topic>Isomerism</topic><topic>Magnetic Resonance Spectroscopy - methods</topic><topic>Models, Chemical</topic><topic>Molecular Conformation</topic><topic>Rhodanine - analogs & derivatives</topic><topic>Rhodanine - chemistry</topic><topic>Rotation</topic><topic>Thermodynamics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Aydeniz, Yeliz</creatorcontrib><creatorcontrib>Oguz, Funda</creatorcontrib><creatorcontrib>Yaman, Arzu</creatorcontrib><creatorcontrib>Konuklar, Aylin Sungur</creatorcontrib><creatorcontrib>Dogan, Ilknur</creatorcontrib><creatorcontrib>Aviyente, Viktorya</creatorcontrib><creatorcontrib>Klein, Roger A</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Organic & biomolecular chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Aydeniz, Yeliz</au><au>Oguz, Funda</au><au>Yaman, Arzu</au><au>Konuklar, Aylin Sungur</au><au>Dogan, Ilknur</au><au>Aviyente, Viktorya</au><au>Klein, Roger A</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Barriers to internal rotation around the C-N bond in 3-(o-aryl)-5-methyl-rhodanines using NMR spectroscopy and computational studies. Electron density topological analysis of the transition states</atitle><jtitle>Organic & biomolecular chemistry</jtitle><addtitle>Org Biomol Chem</addtitle><date>2004-09-07</date><risdate>2004</risdate><volume>2</volume><issue>17</issue><spage>2426</spage><epage>2436</epage><pages>2426-2436</pages><issn>1477-0520</issn><eissn>1477-0539</eissn><abstract>We have investigated the pairs of rotational isomers for six 3-(o-aryl)-5-methyl-rhodanines (Z = H, F, Cl, Br, OH, and CH3) using NMR spectroscopy and density functional theory (DFT) calculations. Electron density topological and NBO analysis has demonstrated the importance of non-covalent interactions, characterised by (3, -1) bond critical points (BCPs), between the oxygen and sulfur atoms on the thiazolidine ring with the aryl substitutents in stabilizing the transition states. The energetic activation barriers to rotation have also been determined using computational results; rotational barriers for 3-(o-chlorophenyl)-5-methyl-rhodanine (3S) and 3-(o-tolyl)-5-methyl-rhodanine (6S) were determined experimentally based on NMR separation of the diastereoisomeric pairs, and the first-order rate constants used to derive the value of the rotational barrier from the Eyring equation.</abstract><cop>England</cop><pmid>15326522</pmid><doi>10.1039/B406556E</doi><tpages>11</tpages></addata></record> |
| fulltext | fulltext |
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| ispartof | Organic & biomolecular chemistry, 2004-09, Vol.2 (17), p.2426-2436 |
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| source | Royal Society of Chemistry Journals Archive (1841-2007); MEDLINE; Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Computer Simulation Electrons Isomerism Magnetic Resonance Spectroscopy - methods Models, Chemical Molecular Conformation Rhodanine - analogs & derivatives Rhodanine - chemistry Rotation Thermodynamics |
| title | Barriers to internal rotation around the C-N bond in 3-(o-aryl)-5-methyl-rhodanines using NMR spectroscopy and computational studies. Electron density topological analysis of the transition states |
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