Cleavage of Both C(sp3)−C(sp2) Bonds of Alkylidenecyclopropanes: Formation of Ethylene−Osmium−Vinylidene Complexes

The complex [OsTp(κ1-OCMe)2(PiPr3)]BF4 [Tp = hydridotris(pyrazolyl)borate] promotes the cleavage of both C(sp3)−C(sp2) bonds of benzylidenecyclopropane and 3-phenylpropylidenecyclopropane to yield the complexes [OsTp(CCHR)(η2-CH2CH2)(PiPr3)]BF4 (R = Ph, CH2CH2Ph). The process is proposed to take...

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Veröffentlicht in:	Journal of the American Chemical Society 2010-01, Vol.132 (2), p.454-455
Hauptverfasser:	Castro-Rodrigo, Ruth, Esteruelas, Miguel A, López, Ana M, López, Fernando, Mascareñas, José L, Oliván, Montserrat, Oñate, Enrique, Saya, Lucía, Villarino, Lara
Format:	Artikel
Sprache:	eng
Schlagworte:	Crystallography, X-Ray Cyclopropanes - chemistry Ethylenes - chemistry Models, Molecular Molecular Conformation Organometallic Compounds - chemistry Osmium - chemistry Stereoisomerism Thermodynamics Vinyl Compounds - chemistry
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container_title	Journal of the American Chemical Society
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creator	Castro-Rodrigo, Ruth Esteruelas, Miguel A López, Ana M López, Fernando Mascareñas, José L Oliván, Montserrat Oñate, Enrique Saya, Lucía Villarino, Lara
description	The complex [OsTp(κ1-OCMe)2(PiPr3)]BF4 [Tp = hydridotris(pyrazolyl)borate] promotes the cleavage of both C(sp3)−C(sp2) bonds of benzylidenecyclopropane and 3-phenylpropylidenecyclopropane to yield the complexes [OsTp(CCHR)(η2-CH2CH2)(PiPr3)]BF4 (R = Ph, CH2CH2Ph). The process is proposed to take place via metallacyclopropene intermediates stabilized by an ethylene chelation assistant. The driving force for the fragmentation is the high stability of the resulting ethylene−Os−vinylidene species.
doi_str_mv	10.1021/ja909240q
format	Article
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Am. Chem. Soc</addtitle><description>The complex [OsTp(κ1-OCMe)2(PiPr3)]BF4 [Tp = hydridotris(pyrazolyl)borate] promotes the cleavage of both C(sp3)−C(sp2) bonds of benzylidenecyclopropane and 3-phenylpropylidenecyclopropane to yield the complexes [OsTp(CCHR)(η2-CH2CH2)(PiPr3)]BF4 (R = Ph, CH2CH2Ph). The process is proposed to take place via metallacyclopropene intermediates stabilized by an ethylene chelation assistant. The driving force for the fragmentation is the high stability of the resulting ethylene−Os−vinylidene species.</description><subject>Crystallography, X-Ray</subject><subject>Cyclopropanes - chemistry</subject><subject>Ethylenes - chemistry</subject><subject>Models, Molecular</subject><subject>Molecular Conformation</subject><subject>Organometallic Compounds - chemistry</subject><subject>Osmium - chemistry</subject><subject>Stereoisomerism</subject><subject>Thermodynamics</subject><subject>Vinyl Compounds - chemistry</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkLtOwzAUhi0EoqUw8AIoC4IOAV-SJmYrUQtIlboAa-T4QlOcOMQJat6AmUfkSXDU0onp3L7z65wfgHMEbxDE6HbNKKQ4gB8HYIhCDP0Q4ckhGEIIsR_FEzIAJ9auXRngGB2DAYYQRWGIh2CTaMk-2Zv0jPLuTbPykmtbkfHP13ef4LFrlsL206l-73QuZCl5x7WpalOxUto7b27qgjW5KXtq1qw67RgnsLRF3hYuec3L3aaXmKLSciPtKThSTFt5tosj8DKfPSeP_mL58JRMFz4jMWz8QNGIQxTzjEooM0GoEFhksaAsVJyHguIMwUhRFiClwljSgGFMJizg7lukyAhcbXXdvR-ttE1a5JZLrd3tprVpREiMIKXYkeMtyWtjbS1VWtV5weouRTDtfU73Pjv2YqfaZoUUe_LPWAdcbgHGbbo2bV26J_8R-gXBxIgR</recordid><startdate>20100120</startdate><enddate>20100120</enddate><creator>Castro-Rodrigo, Ruth</creator><creator>Esteruelas, Miguel A</creator><creator>López, Ana M</creator><creator>López, Fernando</creator><creator>Mascareñas, José L</creator><creator>Oliván, Montserrat</creator><creator>Oñate, Enrique</creator><creator>Saya, Lucía</creator><creator>Villarino, Lara</creator><general>American Chemical Society</general><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>20100120</creationdate><title>Cleavage of Both C(sp3)−C(sp2) Bonds of Alkylidenecyclopropanes: Formation of Ethylene−Osmium−Vinylidene Complexes</title><author>Castro-Rodrigo, Ruth ; Esteruelas, Miguel A ; López, Ana M ; López, Fernando ; Mascareñas, José L ; Oliván, Montserrat ; Oñate, Enrique ; Saya, Lucía ; Villarino, Lara</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a380t-4f97c018cb9e0ebd39dd2db8d9a5fcc5d92b107f9a41ff58e94a2236a4c0041f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><topic>Crystallography, X-Ray</topic><topic>Cyclopropanes - chemistry</topic><topic>Ethylenes - chemistry</topic><topic>Models, Molecular</topic><topic>Molecular Conformation</topic><topic>Organometallic Compounds - chemistry</topic><topic>Osmium - chemistry</topic><topic>Stereoisomerism</topic><topic>Thermodynamics</topic><topic>Vinyl Compounds - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Castro-Rodrigo, Ruth</creatorcontrib><creatorcontrib>Esteruelas, Miguel A</creatorcontrib><creatorcontrib>López, Ana M</creatorcontrib><creatorcontrib>López, Fernando</creatorcontrib><creatorcontrib>Mascareñas, José L</creatorcontrib><creatorcontrib>Oliván, Montserrat</creatorcontrib><creatorcontrib>Oñate, Enrique</creatorcontrib><creatorcontrib>Saya, Lucía</creatorcontrib><creatorcontrib>Villarino, Lara</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>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Castro-Rodrigo, Ruth</au><au>Esteruelas, Miguel A</au><au>López, Ana M</au><au>López, Fernando</au><au>Mascareñas, José L</au><au>Oliván, Montserrat</au><au>Oñate, Enrique</au><au>Saya, Lucía</au><au>Villarino, Lara</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Cleavage of Both C(sp3)−C(sp2) Bonds of Alkylidenecyclopropanes: Formation of Ethylene−Osmium−Vinylidene Complexes</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2010-01-20</date><risdate>2010</risdate><volume>132</volume><issue>2</issue><spage>454</spage><epage>455</epage><pages>454-455</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>The complex [OsTp(κ1-OCMe)2(PiPr3)]BF4 [Tp = hydridotris(pyrazolyl)borate] promotes the cleavage of both C(sp3)−C(sp2) bonds of benzylidenecyclopropane and 3-phenylpropylidenecyclopropane to yield the complexes [OsTp(CCHR)(η2-CH2CH2)(PiPr3)]BF4 (R = Ph, CH2CH2Ph). The process is proposed to take place via metallacyclopropene intermediates stabilized by an ethylene chelation assistant. The driving force for the fragmentation is the high stability of the resulting ethylene−Os−vinylidene species.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>20017552</pmid><doi>10.1021/ja909240q</doi><tpages>2</tpages></addata></record>
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source	MEDLINE; ACS Journals: American Chemical Society Web Editions
subjects	Crystallography, X-Ray Cyclopropanes - chemistry Ethylenes - chemistry Models, Molecular Molecular Conformation Organometallic Compounds - chemistry Osmium - chemistry Stereoisomerism Thermodynamics Vinyl Compounds - chemistry
title	Cleavage of Both C(sp3)−C(sp2) Bonds of Alkylidenecyclopropanes: Formation of Ethylene−Osmium−Vinylidene Complexes
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