CO2 Adducts of N-Heterocyclic Carbenes: Thermal Stability and Catalytic Activity toward the Coupling of CO2 with Epoxides
Thermal stability of CO2 adducts of N-heterocyclic carbenes (NHCs) was studied by means of in situ FTIR method with monitoring of the ν(CO2) region of the infrared spectra under various conditions. 1,3-Bis(2,6-diisopropylphenyl)imidazolinium-2-carboxylate (SIPr-CO2) shows higher thermal stability co...
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| Veröffentlicht in: | Journal of organic chemistry 2008-10, Vol.73 (20), p.8039-8044 |
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| creator | Zhou, Hui Zhang, Wen-Zhen Liu, Cui-Hua Qu, Jing-Ping Lu, Xiao-Bing |
| description | Thermal stability of CO2 adducts of N-heterocyclic carbenes (NHCs) was studied by means of in situ FTIR method with monitoring of the ν(CO2) region of the infrared spectra under various conditions. 1,3-Bis(2,6-diisopropylphenyl)imidazolinium-2-carboxylate (SIPr-CO2) shows higher thermal stability compared with 1,3-bis(2,6-diisopropylphenyl)imidazolium-2-carboxylate (IPr-CO2). The presence of free CO2 can significantly inhibit the decomposition of NHC-CO2 adducts, while the addition of an epoxide such as propylene oxide has a negative effect on stabilizing these adducts. As zwitterionic compounds, NHC-CO2 adducts were also proved to be effective organic catalysts for the coupling reaction of CO2 and epoxides to afford cyclic carbonates, for which a possible mechanism was proposed. Among these NHC-CO2 adducts, the relatively unstable IPr-CO2 exhibits the highest catalytic activity. The presence of an electrophile such as SalenAlEt could greatly improve the catalytic activity of IPr-CO2 due to intermolecular cooperative catalysis of the binary components. |
| doi_str_mv | 10.1021/jo801457r |
| format | Article |
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The presence of free CO2 can significantly inhibit the decomposition of NHC-CO2 adducts, while the addition of an epoxide such as propylene oxide has a negative effect on stabilizing these adducts. As zwitterionic compounds, NHC-CO2 adducts were also proved to be effective organic catalysts for the coupling reaction of CO2 and epoxides to afford cyclic carbonates, for which a possible mechanism was proposed. Among these NHC-CO2 adducts, the relatively unstable IPr-CO2 exhibits the highest catalytic activity. The presence of an electrophile such as SalenAlEt could greatly improve the catalytic activity of IPr-CO2 due to intermolecular cooperative catalysis of the binary components.</description><identifier>ISSN: 0022-3263</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/jo801457r</identifier><identifier>PMID: 18788780</identifier><identifier>CODEN: JOCEAH</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Catalysis ; Catalysts: preparations and properties ; Chemistry ; Exact sciences and technology ; General and physical chemistry ; Heterocyclic compounds ; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives ; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings ; Kinetics and mechanisms ; Organic chemistry ; Preparations and properties ; Reactivity and mechanisms ; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</subject><ispartof>Journal of organic chemistry, 2008-10, Vol.73 (20), p.8039-8044</ispartof><rights>Copyright © 2008 American Chemical Society</rights><rights>2009 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jo801457r$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jo801457r$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,27075,27923,27924,56737,56787</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=20775501$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/18788780$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Zhou, Hui</creatorcontrib><creatorcontrib>Zhang, Wen-Zhen</creatorcontrib><creatorcontrib>Liu, Cui-Hua</creatorcontrib><creatorcontrib>Qu, Jing-Ping</creatorcontrib><creatorcontrib>Lu, Xiao-Bing</creatorcontrib><title>CO2 Adducts of N-Heterocyclic Carbenes: Thermal Stability and Catalytic Activity toward the Coupling of CO2 with Epoxides</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>Thermal stability of CO2 adducts of N-heterocyclic carbenes (NHCs) was studied by means of in situ FTIR method with monitoring of the ν(CO2) region of the infrared spectra under various conditions. 1,3-Bis(2,6-diisopropylphenyl)imidazolinium-2-carboxylate (SIPr-CO2) shows higher thermal stability compared with 1,3-bis(2,6-diisopropylphenyl)imidazolium-2-carboxylate (IPr-CO2). The presence of free CO2 can significantly inhibit the decomposition of NHC-CO2 adducts, while the addition of an epoxide such as propylene oxide has a negative effect on stabilizing these adducts. As zwitterionic compounds, NHC-CO2 adducts were also proved to be effective organic catalysts for the coupling reaction of CO2 and epoxides to afford cyclic carbonates, for which a possible mechanism was proposed. Among these NHC-CO2 adducts, the relatively unstable IPr-CO2 exhibits the highest catalytic activity. The presence of an electrophile such as SalenAlEt could greatly improve the catalytic activity of IPr-CO2 due to intermolecular cooperative catalysis of the binary components.</description><subject>Catalysis</subject><subject>Catalysts: preparations and properties</subject><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>General and physical chemistry</subject><subject>Heterocyclic compounds</subject><subject>Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives</subject><subject>Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings</subject><subject>Kinetics and mechanisms</subject><subject>Organic chemistry</subject><subject>Preparations and properties</subject><subject>Reactivity and mechanisms</subject><subject>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</subject><issn>0022-3263</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2008</creationdate><recordtype>article</recordtype><recordid>eNpFkU9v1DAQxS0EokvhwBdAvsAt1HFiO-a2RP2DVLUVXS5crIntsF68yWI7tPn2eNXtMhpppHk_vZHeIPS-JJ9LQsuzzdiQsmYivECLklFScEnql2hBCKVFRXl1gt7EuCG5GGOv0UnZiCY3WaC5vaV4acykU8Rjj2-KK5tsGPWsvdO4hdDZwcYveLW2YQse3yfonHdpxjCYrCfwc8rkUif3d79O4wMEg9Pa4nacdt4Nv_bG-zsPLq3x-W58dMbGt-hVDz7ad4d5in5cnK_aq-L69vJbu7wuoCIiFUYSyqW0FogwoIF2TcOYlkIYQhpWS8t517EMg-ybOot1A31PwbKaAZfVKfr05LsL45_JxqS2LmrrPQx2nKLiktdScpbBDwdw6rbWqF1wWwizeg4rAx8PAEQNvg8waBePHCVCMEbKzBVPnIvJPh51CL8VF5VganV3r9rLVX3xvfyqfv73BR3VZpzCkPNQJVH756rjc6t_phqSlg</recordid><startdate>20081017</startdate><enddate>20081017</enddate><creator>Zhou, Hui</creator><creator>Zhang, Wen-Zhen</creator><creator>Liu, Cui-Hua</creator><creator>Qu, Jing-Ping</creator><creator>Lu, Xiao-Bing</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>NPM</scope><scope>7X8</scope></search><sort><creationdate>20081017</creationdate><title>CO2 Adducts of N-Heterocyclic Carbenes: Thermal Stability and Catalytic Activity toward the Coupling of CO2 with Epoxides</title><author>Zhou, Hui ; Zhang, Wen-Zhen ; Liu, Cui-Hua ; Qu, Jing-Ping ; Lu, Xiao-Bing</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a307t-d902699eea07daca2b8855c977d008549e66bb5a30a9f8488548aff2ae545a693</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2008</creationdate><topic>Catalysis</topic><topic>Catalysts: preparations and properties</topic><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>General and physical chemistry</topic><topic>Heterocyclic compounds</topic><topic>Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives</topic><topic>Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings</topic><topic>Kinetics and mechanisms</topic><topic>Organic chemistry</topic><topic>Preparations and properties</topic><topic>Reactivity and mechanisms</topic><topic>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zhou, Hui</creatorcontrib><creatorcontrib>Zhang, Wen-Zhen</creatorcontrib><creatorcontrib>Liu, Cui-Hua</creatorcontrib><creatorcontrib>Qu, Jing-Ping</creatorcontrib><creatorcontrib>Lu, Xiao-Bing</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>PubMed</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zhou, Hui</au><au>Zhang, Wen-Zhen</au><au>Liu, Cui-Hua</au><au>Qu, Jing-Ping</au><au>Lu, Xiao-Bing</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>CO2 Adducts of N-Heterocyclic Carbenes: Thermal Stability and Catalytic Activity toward the Coupling of CO2 with Epoxides</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2008-10-17</date><risdate>2008</risdate><volume>73</volume><issue>20</issue><spage>8039</spage><epage>8044</epage><pages>8039-8044</pages><issn>0022-3263</issn><eissn>1520-6904</eissn><coden>JOCEAH</coden><abstract>Thermal stability of CO2 adducts of N-heterocyclic carbenes (NHCs) was studied by means of in situ FTIR method with monitoring of the ν(CO2) region of the infrared spectra under various conditions. 1,3-Bis(2,6-diisopropylphenyl)imidazolinium-2-carboxylate (SIPr-CO2) shows higher thermal stability compared with 1,3-bis(2,6-diisopropylphenyl)imidazolium-2-carboxylate (IPr-CO2). The presence of free CO2 can significantly inhibit the decomposition of NHC-CO2 adducts, while the addition of an epoxide such as propylene oxide has a negative effect on stabilizing these adducts. As zwitterionic compounds, NHC-CO2 adducts were also proved to be effective organic catalysts for the coupling reaction of CO2 and epoxides to afford cyclic carbonates, for which a possible mechanism was proposed. Among these NHC-CO2 adducts, the relatively unstable IPr-CO2 exhibits the highest catalytic activity. The presence of an electrophile such as SalenAlEt could greatly improve the catalytic activity of IPr-CO2 due to intermolecular cooperative catalysis of the binary components.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>18788780</pmid><doi>10.1021/jo801457r</doi><tpages>6</tpages></addata></record> |
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| subjects | Catalysis Catalysts: preparations and properties Chemistry Exact sciences and technology General and physical chemistry Heterocyclic compounds Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings Kinetics and mechanisms Organic chemistry Preparations and properties Reactivity and mechanisms Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry |
| title | CO2 Adducts of N-Heterocyclic Carbenes: Thermal Stability and Catalytic Activity toward the Coupling of CO2 with Epoxides |
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