Evidence for a Rapid Degenerate Hetero-Cope-Type Rearrangement in [CpW(S)2S-CH2-CHCH2]
Treatment of the salt [PPh4]+[Cp*W(S)3]− (6) with allyl bromide gave the neutral complex [Cp*W(S)2S‐CH2‐CHCH2] (7). The product 7 was characterized by an X‐ray crystal structure analysis. Complex 7 features dynamic NMR spectra that indicate a rapid allyl automerization process. From the analysis of...
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| Veröffentlicht in: | Chemistry, an Asian journal an Asian journal, 2009-12, Vol.4 (12), p.1830-1833 |
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| creator | Eweiner, Florian Senda, Shunsuke Bergander, Klaus Mück-Lichtenfeld, Christian Grimme, Stefan Fröhlich, Roland Aoyama, Michiko Kawaguchi, Hiroyuki Ohki, Yasuhiro Matsumoto, Tsuyoshi Kehr, Gerald Tatsumi, Kazuyuki Erker, Gerhard |
| description | Treatment of the salt [PPh4]+[Cp*W(S)3]− (6) with allyl bromide gave the neutral complex [Cp*W(S)2S‐CH2‐CHCH2] (7). The product 7 was characterized by an X‐ray crystal structure analysis. Complex 7 features dynamic NMR spectra that indicate a rapid allyl automerization process. From the analysis of the temperature‐dependent NMR spectra a Gibbs activation energy of ΔG≠ (278 K)≈13.7±0.1 kcal mol−1 was obtained [ΔH≠≈10.4±0.1 kcal mol−1; ΔS≠≈−11.4 cal mol−1 K−1]. The DFT calculation identified an energetically unfavorable four‐membered transition state of the “forbidden” reaction and a favorable six‐membered transition state of the “Cope‐type” allyl rearrangement process at this transition‐metal complex core.
Allyl automerization: The title complex undergoes rapid allyl automerization, proceeding via a six‐membered transition state, as identified by DFT calculations. A detailed temperature‐dependent NMR study provides a Gibbs activation energy of about 14 kcal mol−1. |
| doi_str_mv | 10.1002/asia.200900360 |
| format | Article |
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Allyl automerization: The title complex undergoes rapid allyl automerization, proceeding via a six‐membered transition state, as identified by DFT calculations. A detailed temperature‐dependent NMR study provides a Gibbs activation energy of about 14 kcal mol−1.</description><identifier>ISSN: 1861-4728</identifier><identifier>EISSN: 1861-471X</identifier><identifier>DOI: 10.1002/asia.200900360</identifier><identifier>PMID: 19885900</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>allyl ligands ; automerization ; density functional calculations ; fluxionality ; tungsten</subject><ispartof>Chemistry, an Asian journal, 2009-12, Vol.4 (12), p.1830-1833</ispartof><rights>Copyright © 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c3370-e0a58359378af1c45f1c9c7979125dfd22736925ff6901ed885f3fe00079ac83</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fasia.200900360$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fasia.200900360$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/19885900$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Eweiner, Florian</creatorcontrib><creatorcontrib>Senda, Shunsuke</creatorcontrib><creatorcontrib>Bergander, Klaus</creatorcontrib><creatorcontrib>Mück-Lichtenfeld, Christian</creatorcontrib><creatorcontrib>Grimme, Stefan</creatorcontrib><creatorcontrib>Fröhlich, Roland</creatorcontrib><creatorcontrib>Aoyama, Michiko</creatorcontrib><creatorcontrib>Kawaguchi, Hiroyuki</creatorcontrib><creatorcontrib>Ohki, Yasuhiro</creatorcontrib><creatorcontrib>Matsumoto, Tsuyoshi</creatorcontrib><creatorcontrib>Kehr, Gerald</creatorcontrib><creatorcontrib>Tatsumi, Kazuyuki</creatorcontrib><creatorcontrib>Erker, Gerhard</creatorcontrib><title>Evidence for a Rapid Degenerate Hetero-Cope-Type Rearrangement in [CpW(S)2S-CH2-CHCH2]</title><title>Chemistry, an Asian journal</title><addtitle>Chemistry - An Asian Journal</addtitle><description>Treatment of the salt [PPh4]+[Cp*W(S)3]− (6) with allyl bromide gave the neutral complex [Cp*W(S)2S‐CH2‐CHCH2] (7). The product 7 was characterized by an X‐ray crystal structure analysis. Complex 7 features dynamic NMR spectra that indicate a rapid allyl automerization process. From the analysis of the temperature‐dependent NMR spectra a Gibbs activation energy of ΔG≠ (278 K)≈13.7±0.1 kcal mol−1 was obtained [ΔH≠≈10.4±0.1 kcal mol−1; ΔS≠≈−11.4 cal mol−1 K−1]. The DFT calculation identified an energetically unfavorable four‐membered transition state of the “forbidden” reaction and a favorable six‐membered transition state of the “Cope‐type” allyl rearrangement process at this transition‐metal complex core.
Allyl automerization: The title complex undergoes rapid allyl automerization, proceeding via a six‐membered transition state, as identified by DFT calculations. A detailed temperature‐dependent NMR study provides a Gibbs activation energy of about 14 kcal mol−1.</description><subject>allyl ligands</subject><subject>automerization</subject><subject>density functional calculations</subject><subject>fluxionality</subject><subject>tungsten</subject><issn>1861-4728</issn><issn>1861-471X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2009</creationdate><recordtype>article</recordtype><recordid>eNqFkM1OGzEUha2KqqSULctqdtDFpNc2HtvLZAgECRWVREoLQpY7cx1Nm_nBngB5nr5HX6mv0IkShe5Y3HvP4jtHV4eQIwp9CsA-21DYPgPQADyBN6RHVULjU0m_7e00U_vkfQg_AQQDrd6RfaqVEp2lR76PHoscqwwjV_vIRje2KfLoDOdYobctRmNs0ddxWjcYT1cNRjdovbfVHEus2qiooru0mZ1MPrFJnI5ZN39__-nE_Qfy1tlFwMPtPSDT89E0HcdX1xeX6eAqzjiXECNYobjQXCrraHYquqUzqaWmTOQuZ0zyRDPhXKKBYt497rhDAJDaZoofkONNbOPrhyWG1pRFyHCxsBXWy2Ak5xqkYroj-xsy83UIHp1pfFFavzIUzLpMsy7T7MrsDB-30csfJeYv-La9DtAb4KlY4OqVODOYXA7-D4833iK0-LzzWv_LJJJLYWZfLsxXDmI4vE3NmP8Di_KN4w</recordid><startdate>20091201</startdate><enddate>20091201</enddate><creator>Eweiner, Florian</creator><creator>Senda, Shunsuke</creator><creator>Bergander, Klaus</creator><creator>Mück-Lichtenfeld, Christian</creator><creator>Grimme, Stefan</creator><creator>Fröhlich, Roland</creator><creator>Aoyama, Michiko</creator><creator>Kawaguchi, Hiroyuki</creator><creator>Ohki, Yasuhiro</creator><creator>Matsumoto, Tsuyoshi</creator><creator>Kehr, Gerald</creator><creator>Tatsumi, Kazuyuki</creator><creator>Erker, Gerhard</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20091201</creationdate><title>Evidence for a Rapid Degenerate Hetero-Cope-Type Rearrangement in [CpW(S)2S-CH2-CHCH2]</title><author>Eweiner, Florian ; Senda, Shunsuke ; Bergander, Klaus ; Mück-Lichtenfeld, Christian ; Grimme, Stefan ; Fröhlich, Roland ; Aoyama, Michiko ; Kawaguchi, Hiroyuki ; Ohki, Yasuhiro ; Matsumoto, Tsuyoshi ; Kehr, Gerald ; Tatsumi, Kazuyuki ; Erker, Gerhard</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3370-e0a58359378af1c45f1c9c7979125dfd22736925ff6901ed885f3fe00079ac83</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2009</creationdate><topic>allyl ligands</topic><topic>automerization</topic><topic>density functional calculations</topic><topic>fluxionality</topic><topic>tungsten</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Eweiner, Florian</creatorcontrib><creatorcontrib>Senda, Shunsuke</creatorcontrib><creatorcontrib>Bergander, Klaus</creatorcontrib><creatorcontrib>Mück-Lichtenfeld, Christian</creatorcontrib><creatorcontrib>Grimme, Stefan</creatorcontrib><creatorcontrib>Fröhlich, Roland</creatorcontrib><creatorcontrib>Aoyama, Michiko</creatorcontrib><creatorcontrib>Kawaguchi, Hiroyuki</creatorcontrib><creatorcontrib>Ohki, Yasuhiro</creatorcontrib><creatorcontrib>Matsumoto, Tsuyoshi</creatorcontrib><creatorcontrib>Kehr, Gerald</creatorcontrib><creatorcontrib>Tatsumi, Kazuyuki</creatorcontrib><creatorcontrib>Erker, Gerhard</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry, an Asian journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Eweiner, Florian</au><au>Senda, Shunsuke</au><au>Bergander, Klaus</au><au>Mück-Lichtenfeld, Christian</au><au>Grimme, Stefan</au><au>Fröhlich, Roland</au><au>Aoyama, Michiko</au><au>Kawaguchi, Hiroyuki</au><au>Ohki, Yasuhiro</au><au>Matsumoto, Tsuyoshi</au><au>Kehr, Gerald</au><au>Tatsumi, Kazuyuki</au><au>Erker, Gerhard</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Evidence for a Rapid Degenerate Hetero-Cope-Type Rearrangement in [CpW(S)2S-CH2-CHCH2]</atitle><jtitle>Chemistry, an Asian journal</jtitle><addtitle>Chemistry - An Asian Journal</addtitle><date>2009-12-01</date><risdate>2009</risdate><volume>4</volume><issue>12</issue><spage>1830</spage><epage>1833</epage><pages>1830-1833</pages><issn>1861-4728</issn><eissn>1861-471X</eissn><abstract>Treatment of the salt [PPh4]+[Cp*W(S)3]− (6) with allyl bromide gave the neutral complex [Cp*W(S)2S‐CH2‐CHCH2] (7). The product 7 was characterized by an X‐ray crystal structure analysis. Complex 7 features dynamic NMR spectra that indicate a rapid allyl automerization process. From the analysis of the temperature‐dependent NMR spectra a Gibbs activation energy of ΔG≠ (278 K)≈13.7±0.1 kcal mol−1 was obtained [ΔH≠≈10.4±0.1 kcal mol−1; ΔS≠≈−11.4 cal mol−1 K−1]. The DFT calculation identified an energetically unfavorable four‐membered transition state of the “forbidden” reaction and a favorable six‐membered transition state of the “Cope‐type” allyl rearrangement process at this transition‐metal complex core.
Allyl automerization: The title complex undergoes rapid allyl automerization, proceeding via a six‐membered transition state, as identified by DFT calculations. A detailed temperature‐dependent NMR study provides a Gibbs activation energy of about 14 kcal mol−1.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>19885900</pmid><doi>10.1002/asia.200900360</doi><tpages>4</tpages></addata></record> |
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| subjects | allyl ligands automerization density functional calculations fluxionality tungsten |
| title | Evidence for a Rapid Degenerate Hetero-Cope-Type Rearrangement in [CpW(S)2S-CH2-CHCH2] |
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