Reactivity of Carbenes and Related Compounds towards Molecular Nitrogen
The thermal N2 exchange of a number of 15N‐labelled diazo compounds was studied in solution. The compounds involved were 3‐diazo‐1‐methylindolin‐2‐one (1), 9‐diazofluorene (2), 5‐diazo‐1,3‐cyclopentadiene‐1,2,3,4‐tetracarbonitrile (3), 2‐diazo‐2H‐imidazole‐4,5‐dicarbonitrile (4), 4‐diazocyclohexa‐2,...
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| Veröffentlicht in: | Helvetica chimica acta 1985-08, Vol.68 (5), p.1427-1443 |
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| container_title | Helvetica chimica acta |
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| creator | Grieve, Duncan M. A. Lewis, Graham E. Ravenscroft, Michael D. Skrabal, Peter Sonoda, Takaaki Szele, Ivanka Zollinger, Heinrich |
| description | The thermal N2 exchange of a number of 15N‐labelled diazo compounds was studied in solution. The compounds involved were 3‐diazo‐1‐methylindolin‐2‐one (1), 9‐diazofluorene (2), 5‐diazo‐1,3‐cyclopentadiene‐1,2,3,4‐tetracarbonitrile (3), 2‐diazo‐2H‐imidazole‐4,5‐dicarbonitrile (4), 4‐diazocyclohexa‐2,5‐dienone (5), and the conjugate acids of 4 and 5, namely 4,5‐dicyano‐1H‐imidazole‐2‐diazonium ion (6) and 4‐hydroxybenzenediazonium ion (7). Only 1, 4, 6, and 7 exchange their diazo group with ‘external’ molecular N2. The results are explained on the hypothesis that only organic species which have an empty σ orbital and which are effective in π electron back‐donation are able to react with N2. Thus, reaction with carbenes is likely to occur only if the carbene is in the 1A2 singlet state and if its electrophilicity is high. |
| doi_str_mv | 10.1002/hlca.19850680534 |
| format | Article |
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A. ; Lewis, Graham E. ; Ravenscroft, Michael D. ; Skrabal, Peter ; Sonoda, Takaaki ; Szele, Ivanka ; Zollinger, Heinrich</creator><creatorcontrib>Grieve, Duncan M. A. ; Lewis, Graham E. ; Ravenscroft, Michael D. ; Skrabal, Peter ; Sonoda, Takaaki ; Szele, Ivanka ; Zollinger, Heinrich</creatorcontrib><description>The thermal N2 exchange of a number of 15N‐labelled diazo compounds was studied in solution. The compounds involved were 3‐diazo‐1‐methylindolin‐2‐one (1), 9‐diazofluorene (2), 5‐diazo‐1,3‐cyclopentadiene‐1,2,3,4‐tetracarbonitrile (3), 2‐diazo‐2H‐imidazole‐4,5‐dicarbonitrile (4), 4‐diazocyclohexa‐2,5‐dienone (5), and the conjugate acids of 4 and 5, namely 4,5‐dicyano‐1H‐imidazole‐2‐diazonium ion (6) and 4‐hydroxybenzenediazonium ion (7). Only 1, 4, 6, and 7 exchange their diazo group with ‘external’ molecular N2. The results are explained on the hypothesis that only organic species which have an empty σ orbital and which are effective in π electron back‐donation are able to react with N2. Thus, reaction with carbenes is likely to occur only if the carbene is in the 1A2 singlet state and if its electrophilicity is high.</description><identifier>ISSN: 0018-019X</identifier><identifier>EISSN: 1522-2675</identifier><identifier>DOI: 10.1002/hlca.19850680534</identifier><identifier>CODEN: HCACAV</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag GmbH</publisher><subject>Chemistry ; Exact sciences and technology ; Labelled compounds chemistry ; Organic chemistry ; Reactivity and mechanisms</subject><ispartof>Helvetica chimica acta, 1985-08, Vol.68 (5), p.1427-1443</ispartof><rights>Copyright © 1985 Verlag GmbH & Co. KGaA, Weinheim</rights><rights>1986 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3644-ea065efe9a79c715cf0d6c5c253626bc873dfa704d07ef4bac40e22962f1c8a23</citedby><cites>FETCH-LOGICAL-c3644-ea065efe9a79c715cf0d6c5c253626bc873dfa704d07ef4bac40e22962f1c8a23</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%2Fhlca.19850680534$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fhlca.19850680534$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27902,27903,45552,45553</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=8688144$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Grieve, Duncan M. A.</creatorcontrib><creatorcontrib>Lewis, Graham E.</creatorcontrib><creatorcontrib>Ravenscroft, Michael D.</creatorcontrib><creatorcontrib>Skrabal, Peter</creatorcontrib><creatorcontrib>Sonoda, Takaaki</creatorcontrib><creatorcontrib>Szele, Ivanka</creatorcontrib><creatorcontrib>Zollinger, Heinrich</creatorcontrib><title>Reactivity of Carbenes and Related Compounds towards Molecular Nitrogen</title><title>Helvetica chimica acta</title><addtitle>HCA</addtitle><description>The thermal N2 exchange of a number of 15N‐labelled diazo compounds was studied in solution. The compounds involved were 3‐diazo‐1‐methylindolin‐2‐one (1), 9‐diazofluorene (2), 5‐diazo‐1,3‐cyclopentadiene‐1,2,3,4‐tetracarbonitrile (3), 2‐diazo‐2H‐imidazole‐4,5‐dicarbonitrile (4), 4‐diazocyclohexa‐2,5‐dienone (5), and the conjugate acids of 4 and 5, namely 4,5‐dicyano‐1H‐imidazole‐2‐diazonium ion (6) and 4‐hydroxybenzenediazonium ion (7). Only 1, 4, 6, and 7 exchange their diazo group with ‘external’ molecular N2. The results are explained on the hypothesis that only organic species which have an empty σ orbital and which are effective in π electron back‐donation are able to react with N2. Thus, reaction with carbenes is likely to occur only if the carbene is in the 1A2 singlet state and if its electrophilicity is high.</description><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Labelled compounds chemistry</subject><subject>Organic chemistry</subject><subject>Reactivity and mechanisms</subject><issn>0018-019X</issn><issn>1522-2675</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1985</creationdate><recordtype>article</recordtype><recordid>eNqFkMFPwjAYxRujiYjePe7gdfi1Xdvt4IEsCiaIkWDk1nx0rU7HRtoh8t8LwRA9eXqX93sv-RFySaFHAdj1W2WwR7NUgExB8OSIdKhgLGZSiWPSAaBpDDSbnZKzEN4BIMtAdchgYtG05WfZbqLGRTn6ua1tiLAuoomtsLVFlDeLZbOqixC1zRr9Nh-ayppVhT4al61vXm19Tk4cVsFe_GSXPN_dTvNhPHoc3Of9UWy4TJLYIkhhnc1QZUZRYRwU0gjDBJdMzk2qeOFQQVKAsi6Zo0nAMpZJ5qhJkfEugf2u8U0I3jq99OUC_UZT0DsReidC_xKxRa72yBKDwcp5rE0ZDlwq05Qmu9rNvrYuK7v5d1YPR3n_702858vQ2q8Dj_5DS8WV0C_jgX5i07vpjM_0kH8DxEKAHQ</recordid><startdate>19850814</startdate><enddate>19850814</enddate><creator>Grieve, Duncan M. A.</creator><creator>Lewis, Graham E.</creator><creator>Ravenscroft, Michael D.</creator><creator>Skrabal, Peter</creator><creator>Sonoda, Takaaki</creator><creator>Szele, Ivanka</creator><creator>Zollinger, Heinrich</creator><general>WILEY-VCH Verlag GmbH</general><general>WILEY‐VCH Verlag GmbH</general><general>Wiley</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19850814</creationdate><title>Reactivity of Carbenes and Related Compounds towards Molecular Nitrogen</title><author>Grieve, Duncan M. A. ; Lewis, Graham E. ; Ravenscroft, Michael D. ; Skrabal, Peter ; Sonoda, Takaaki ; Szele, Ivanka ; Zollinger, Heinrich</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3644-ea065efe9a79c715cf0d6c5c253626bc873dfa704d07ef4bac40e22962f1c8a23</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1985</creationdate><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>Labelled compounds chemistry</topic><topic>Organic chemistry</topic><topic>Reactivity and mechanisms</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Grieve, Duncan M. A.</creatorcontrib><creatorcontrib>Lewis, Graham E.</creatorcontrib><creatorcontrib>Ravenscroft, Michael D.</creatorcontrib><creatorcontrib>Skrabal, Peter</creatorcontrib><creatorcontrib>Sonoda, Takaaki</creatorcontrib><creatorcontrib>Szele, Ivanka</creatorcontrib><creatorcontrib>Zollinger, Heinrich</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><jtitle>Helvetica chimica acta</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Grieve, Duncan M. A.</au><au>Lewis, Graham E.</au><au>Ravenscroft, Michael D.</au><au>Skrabal, Peter</au><au>Sonoda, Takaaki</au><au>Szele, Ivanka</au><au>Zollinger, Heinrich</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reactivity of Carbenes and Related Compounds towards Molecular Nitrogen</atitle><jtitle>Helvetica chimica acta</jtitle><addtitle>HCA</addtitle><date>1985-08-14</date><risdate>1985</risdate><volume>68</volume><issue>5</issue><spage>1427</spage><epage>1443</epage><pages>1427-1443</pages><issn>0018-019X</issn><eissn>1522-2675</eissn><coden>HCACAV</coden><abstract>The thermal N2 exchange of a number of 15N‐labelled diazo compounds was studied in solution. The compounds involved were 3‐diazo‐1‐methylindolin‐2‐one (1), 9‐diazofluorene (2), 5‐diazo‐1,3‐cyclopentadiene‐1,2,3,4‐tetracarbonitrile (3), 2‐diazo‐2H‐imidazole‐4,5‐dicarbonitrile (4), 4‐diazocyclohexa‐2,5‐dienone (5), and the conjugate acids of 4 and 5, namely 4,5‐dicyano‐1H‐imidazole‐2‐diazonium ion (6) and 4‐hydroxybenzenediazonium ion (7). Only 1, 4, 6, and 7 exchange their diazo group with ‘external’ molecular N2. The results are explained on the hypothesis that only organic species which have an empty σ orbital and which are effective in π electron back‐donation are able to react with N2. Thus, reaction with carbenes is likely to occur only if the carbene is in the 1A2 singlet state and if its electrophilicity is high.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag GmbH</pub><doi>10.1002/hlca.19850680534</doi><tpages>17</tpages></addata></record> |
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| ispartof | Helvetica chimica acta, 1985-08, Vol.68 (5), p.1427-1443 |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Chemistry Exact sciences and technology Labelled compounds chemistry Organic chemistry Reactivity and mechanisms |
| title | Reactivity of Carbenes and Related Compounds towards Molecular Nitrogen |
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