Mechanism of C−H Bond Activation/C−C Bond Formation Reaction between Diazo Compound and Alkane Catalyzed by Dirhodium Tetracarboxylate

The B3LYP density functional studies on the dirhodium tetracarboxylate-catalyzed C−H bond activation/C−C bond formation reaction of a diazo compound with an alkane revealed the energetics and the geometry of important intermediates and transition states in the catalytic cycle. The reaction is initia...

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Veröffentlicht in:Journal of the American Chemical Society 2002-06, Vol.124 (24), p.7181-7192
Hauptverfasser: Nakamura, Eiichi, Yoshikai, Naohiko, Yamanaka, Masahiro
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creator Nakamura, Eiichi
Yoshikai, Naohiko
Yamanaka, Masahiro
description The B3LYP density functional studies on the dirhodium tetracarboxylate-catalyzed C−H bond activation/C−C bond formation reaction of a diazo compound with an alkane revealed the energetics and the geometry of important intermediates and transition states in the catalytic cycle. The reaction is initiated by complexation between the rhodium catalyst and the diazo compound. Driven by the back-donation from the Rh 4d xz orbital to the C−N σ*-orbital, nitrogen extrusion takes place to afford a rhodium−carbene complex. The carbene carbon of the complex is strongly electrophilic because of its vacant 2p orbital. The C−H activation/C−C formation proceeds in a single step through a three-centered hydride transfer-like transition state with a small activation energy. Only one of the two rhodium atoms works as a carbene binding site throughout the reaction, and the other rhodium atom assists the C−H insertion reaction. The second Rh atom acts as a mobile ligand for the first one to enhance the electrophilicity of the carbene moiety and to facilitate the cleavage of the rhodium−carbon bond. The calculations reproduce experimental data including the activation enthalpy of the nitrogen extrusion, the kinetic isotope effect of the C−H insertion, and the reactivity order of the C−H bond.
doi_str_mv 10.1021/ja017823o
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The reaction is initiated by complexation between the rhodium catalyst and the diazo compound. Driven by the back-donation from the Rh 4d xz orbital to the C−N σ*-orbital, nitrogen extrusion takes place to afford a rhodium−carbene complex. The carbene carbon of the complex is strongly electrophilic because of its vacant 2p orbital. The C−H activation/C−C formation proceeds in a single step through a three-centered hydride transfer-like transition state with a small activation energy. Only one of the two rhodium atoms works as a carbene binding site throughout the reaction, and the other rhodium atom assists the C−H insertion reaction. The second Rh atom acts as a mobile ligand for the first one to enhance the electrophilicity of the carbene moiety and to facilitate the cleavage of the rhodium−carbon bond. 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Am. Chem. Soc</addtitle><description>The B3LYP density functional studies on the dirhodium tetracarboxylate-catalyzed C−H bond activation/C−C bond formation reaction of a diazo compound with an alkane revealed the energetics and the geometry of important intermediates and transition states in the catalytic cycle. The reaction is initiated by complexation between the rhodium catalyst and the diazo compound. Driven by the back-donation from the Rh 4d xz orbital to the C−N σ*-orbital, nitrogen extrusion takes place to afford a rhodium−carbene complex. The carbene carbon of the complex is strongly electrophilic because of its vacant 2p orbital. The C−H activation/C−C formation proceeds in a single step through a three-centered hydride transfer-like transition state with a small activation energy. Only one of the two rhodium atoms works as a carbene binding site throughout the reaction, and the other rhodium atom assists the C−H insertion reaction. The second Rh atom acts as a mobile ligand for the first one to enhance the electrophilicity of the carbene moiety and to facilitate the cleavage of the rhodium−carbon bond. The calculations reproduce experimental data including the activation enthalpy of the nitrogen extrusion, the kinetic isotope effect of the C−H insertion, and the reactivity order of the C−H bond.</description><subject>Chemistry</subject><subject>Exact sciences and technology</subject><subject>Kinetics and mechanisms</subject><subject>Organic chemistry</subject><subject>Reactivity and mechanisms</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2002</creationdate><recordtype>article</recordtype><recordid>eNpt0Mtu1DAUBmALUdGhsOAFkDcgsUjrS5zLsgRKKw0ClUHqzjqxHdXTJB5sBzp9AsSSR-RJ6umMOhtWto8__bJ_hF5RckwJoydLILSsGHdP0IwKRjJBWfEUzQghLCurgh-i5yEs0zFnFX2GDikjomZ5PkN_Pht1DaMNA3Ydbv79_nuO37tR41MV7U-I1o0nm2mznZ45PzwM8aUB9bBpTfxlzIg_WLhzuHHDyk1Jwiajv4HR4AYi9Os7o3G7TsxfO22nAS9M9KDAt-523UM0L9BBB30wL3frEfp-9nHRnGfzL58umtN5BoKKmNG2yxXZ_KWohSGagSZElboE3XLdKV1zqkEpQ1rQVa10Jyipi0p3neai1PwIvd3mrrz7MZkQ5WCDMn2f3uqmIEtakYKLKsF3W6i8C8GbTq68HcCvJSVyU7x8LD7Z17vQqR2M3std0wm82QEICvrOw6hs2Dtecppzlly2dTZEc_t4D_5GFiUvhVx8_SbFVU3ZnFzJy30uqCCXbvJj6u4_D7wHyV6psQ</recordid><startdate>20020619</startdate><enddate>20020619</enddate><creator>Nakamura, Eiichi</creator><creator>Yoshikai, Naohiko</creator><creator>Yamanaka, Masahiro</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20020619</creationdate><title>Mechanism of C−H Bond Activation/C−C Bond Formation Reaction between Diazo Compound and Alkane Catalyzed by Dirhodium Tetracarboxylate</title><author>Nakamura, Eiichi ; Yoshikai, Naohiko ; Yamanaka, Masahiro</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a515t-1bf4c00004695e0d2ad00c7d7adb3dfcd931dacce0bad89cdf510968dffd357d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2002</creationdate><topic>Chemistry</topic><topic>Exact sciences and technology</topic><topic>Kinetics and mechanisms</topic><topic>Organic chemistry</topic><topic>Reactivity and mechanisms</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Nakamura, Eiichi</creatorcontrib><creatorcontrib>Yoshikai, Naohiko</creatorcontrib><creatorcontrib>Yamanaka, Masahiro</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</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>Nakamura, Eiichi</au><au>Yoshikai, Naohiko</au><au>Yamanaka, Masahiro</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mechanism of C−H Bond Activation/C−C Bond Formation Reaction between Diazo Compound and Alkane Catalyzed by Dirhodium Tetracarboxylate</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2002-06-19</date><risdate>2002</risdate><volume>124</volume><issue>24</issue><spage>7181</spage><epage>7192</epage><pages>7181-7192</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>The B3LYP density functional studies on the dirhodium tetracarboxylate-catalyzed C−H bond activation/C−C bond formation reaction of a diazo compound with an alkane revealed the energetics and the geometry of important intermediates and transition states in the catalytic cycle. The reaction is initiated by complexation between the rhodium catalyst and the diazo compound. Driven by the back-donation from the Rh 4d xz orbital to the C−N σ*-orbital, nitrogen extrusion takes place to afford a rhodium−carbene complex. The carbene carbon of the complex is strongly electrophilic because of its vacant 2p orbital. The C−H activation/C−C formation proceeds in a single step through a three-centered hydride transfer-like transition state with a small activation energy. Only one of the two rhodium atoms works as a carbene binding site throughout the reaction, and the other rhodium atom assists the C−H insertion reaction. The second Rh atom acts as a mobile ligand for the first one to enhance the electrophilicity of the carbene moiety and to facilitate the cleavage of the rhodium−carbon bond. The calculations reproduce experimental data including the activation enthalpy of the nitrogen extrusion, the kinetic isotope effect of the C−H insertion, and the reactivity order of the C−H bond.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>12059244</pmid><doi>10.1021/ja017823o</doi><tpages>12</tpages></addata></record>
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subjects Chemistry
Exact sciences and technology
Kinetics and mechanisms
Organic chemistry
Reactivity and mechanisms
title Mechanism of C−H Bond Activation/C−C Bond Formation Reaction between Diazo Compound and Alkane Catalyzed by Dirhodium Tetracarboxylate
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