The Catalytic Dehydrogenation of Ammonia-Borane Involving an Unexpected Hydrogen Transfer to Ligated Carbene and Subsequent Carbon−Hydrogen Activation
Density functional Tao−Perdew−Staroverov−Scuseria calculations with all-electron correlation-consistent polarized valence double-ζ basis set demonstrate that N-heterocyclic carbene (NHC) nickel complexes catalyze the dehydrogenation of ammonia-borane, a candidate for chemical hydrogen storage, throu...
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| Veröffentlicht in: | Journal of the American Chemical Society 2008-02, Vol.130 (6), p.1798-1799 |
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| container_title | Journal of the American Chemical Society |
| container_volume | 130 |
| creator | Yang, Xinzheng Hall, Michael B |
| description | Density functional Tao−Perdew−Staroverov−Scuseria calculations with all-electron correlation-consistent polarized valence double-ζ basis set demonstrate that N-heterocyclic carbene (NHC) nickel complexes catalyze the dehydrogenation of ammonia-borane, a candidate for chemical hydrogen storage, through proton transfer from nitrogen to the metal-bound carbene carbon, instead of the B−H or N−H bond activation. This new C−H bond is then activated by the metal, transferring the H to the metal, then forming the H2 by transferring a H from B to the metal, instead the β-H transfer. This reaction pathway explains the importance of the NHC ligands in the dehydrogenation and points the way to finding new catalyst with higher efficiency, as partial unsaturation of the M-L bond may be essential for rapid H transfers. |
| doi_str_mv | 10.1021/ja0751328 |
| format | Article |
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This new C−H bond is then activated by the metal, transferring the H to the metal, then forming the H2 by transferring a H from B to the metal, instead the β-H transfer. This reaction pathway explains the importance of the NHC ligands in the dehydrogenation and points the way to finding new catalyst with higher efficiency, as partial unsaturation of the M-L bond may be essential for rapid H transfers.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja0751328</identifier><identifier>PMID: 18211066</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Ammonia - chemistry ; Boranes - chemistry ; Catalysis ; Computer Simulation ; Hydrocarbons - chemistry ; Hydrogen - chemistry ; Hydrogenation ; Ligands ; Methane - analogs & derivatives ; Methane - chemistry ; Models, Chemical ; Nickel - chemistry ; Organometallic Compounds - chemistry ; Quantum Theory</subject><ispartof>Journal of the American Chemical Society, 2008-02, Vol.130 (6), p.1798-1799</ispartof><rights>Copyright © 2008 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a417t-f73afcfb6424843c25ef894162bf2183206f808a864aab2002e809882f320e493</citedby><cites>FETCH-LOGICAL-a417t-f73afcfb6424843c25ef894162bf2183206f808a864aab2002e809882f320e493</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja0751328$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja0751328$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>315,781,785,2766,27078,27926,27927,56740,56790</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/18211066$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Yang, Xinzheng</creatorcontrib><creatorcontrib>Hall, Michael B</creatorcontrib><title>The Catalytic Dehydrogenation of Ammonia-Borane Involving an Unexpected Hydrogen Transfer to Ligated Carbene and Subsequent Carbon−Hydrogen Activation</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>Density functional Tao−Perdew−Staroverov−Scuseria calculations with all-electron correlation-consistent polarized valence double-ζ basis set demonstrate that N-heterocyclic carbene (NHC) nickel complexes catalyze the dehydrogenation of ammonia-borane, a candidate for chemical hydrogen storage, through proton transfer from nitrogen to the metal-bound carbene carbon, instead of the B−H or N−H bond activation. This new C−H bond is then activated by the metal, transferring the H to the metal, then forming the H2 by transferring a H from B to the metal, instead the β-H transfer. This reaction pathway explains the importance of the NHC ligands in the dehydrogenation and points the way to finding new catalyst with higher efficiency, as partial unsaturation of the M-L bond may be essential for rapid H transfers.</description><subject>Ammonia - chemistry</subject><subject>Boranes - chemistry</subject><subject>Catalysis</subject><subject>Computer Simulation</subject><subject>Hydrocarbons - chemistry</subject><subject>Hydrogen - chemistry</subject><subject>Hydrogenation</subject><subject>Ligands</subject><subject>Methane - analogs & derivatives</subject><subject>Methane - chemistry</subject><subject>Models, Chemical</subject><subject>Nickel - chemistry</subject><subject>Organometallic Compounds - chemistry</subject><subject>Quantum Theory</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2008</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkcGO0zAQhi0EYsvCgRdAvoDEIWA7ieMeS2HZlYpA2ixXa5KOuymJ3bWdavsGnDnxfDwJ7rYqF06W_X__zPgfQl5y9o4zwd-vgVUlz4V6RCa8FCwruZCPyYQxJrJKyfyMPAthna6FUPwpOeNKcM6knJDf9S3SOUTod7Fr6Ue83S29W6GF2DlLnaGzYXC2g-yD82CRXtmt67edXVGw9Mbi_QbbiEt6efTROmHBoKfR0UW3gr04B99gMoNd0uuxCXg3oo0Pz87--fnrZJ61sds-tH5OnhjoA744nufk5uJTPb_MFl8_X81niwwKXsXMVDmY1jSyEIUq8laUaNS04FI0RnCVCyaNYgqULAAakQJBxaZKCZMkLKb5OXlzqLvxLk0Voh660GLfp8-6MeiKiYrxfA--PYCtdyF4NHrjuwH8TnOm92vQpzUk9tWx6NgMuPxHHnNPQHYAuhDx_qSD_6FllVelrr9d64u8lsWXqdLfE__6wEMb9NqN3qZM_tP4L46Pn3A</recordid><startdate>20080213</startdate><enddate>20080213</enddate><creator>Yang, Xinzheng</creator><creator>Hall, Michael B</creator><general>American Chemical Society</general><scope>BSCLL</scope><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>20080213</creationdate><title>The Catalytic Dehydrogenation of Ammonia-Borane Involving an Unexpected Hydrogen Transfer to Ligated Carbene and Subsequent Carbon−Hydrogen Activation</title><author>Yang, Xinzheng ; Hall, Michael B</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a417t-f73afcfb6424843c25ef894162bf2183206f808a864aab2002e809882f320e493</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2008</creationdate><topic>Ammonia - chemistry</topic><topic>Boranes - chemistry</topic><topic>Catalysis</topic><topic>Computer Simulation</topic><topic>Hydrocarbons - chemistry</topic><topic>Hydrogen - chemistry</topic><topic>Hydrogenation</topic><topic>Ligands</topic><topic>Methane - analogs & derivatives</topic><topic>Methane - chemistry</topic><topic>Models, Chemical</topic><topic>Nickel - chemistry</topic><topic>Organometallic Compounds - chemistry</topic><topic>Quantum Theory</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Yang, Xinzheng</creatorcontrib><creatorcontrib>Hall, Michael B</creatorcontrib><collection>Istex</collection><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>Yang, Xinzheng</au><au>Hall, Michael B</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>The Catalytic Dehydrogenation of Ammonia-Borane Involving an Unexpected Hydrogen Transfer to Ligated Carbene and Subsequent Carbon−Hydrogen Activation</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2008-02-13</date><risdate>2008</risdate><volume>130</volume><issue>6</issue><spage>1798</spage><epage>1799</epage><pages>1798-1799</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Density functional Tao−Perdew−Staroverov−Scuseria calculations with all-electron correlation-consistent polarized valence double-ζ basis set demonstrate that N-heterocyclic carbene (NHC) nickel complexes catalyze the dehydrogenation of ammonia-borane, a candidate for chemical hydrogen storage, through proton transfer from nitrogen to the metal-bound carbene carbon, instead of the B−H or N−H bond activation. This new C−H bond is then activated by the metal, transferring the H to the metal, then forming the H2 by transferring a H from B to the metal, instead the β-H transfer. This reaction pathway explains the importance of the NHC ligands in the dehydrogenation and points the way to finding new catalyst with higher efficiency, as partial unsaturation of the M-L bond may be essential for rapid H transfers.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>18211066</pmid><doi>10.1021/ja0751328</doi><tpages>2</tpages></addata></record> |
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| identifier | ISSN: 0002-7863 |
| ispartof | Journal of the American Chemical Society, 2008-02, Vol.130 (6), p.1798-1799 |
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| language | eng |
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| source | MEDLINE; ACS Publications |
| subjects | Ammonia - chemistry Boranes - chemistry Catalysis Computer Simulation Hydrocarbons - chemistry Hydrogen - chemistry Hydrogenation Ligands Methane - analogs & derivatives Methane - chemistry Models, Chemical Nickel - chemistry Organometallic Compounds - chemistry Quantum Theory |
| title | The Catalytic Dehydrogenation of Ammonia-Borane Involving an Unexpected Hydrogen Transfer to Ligated Carbene and Subsequent Carbon−Hydrogen Activation |
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