Reversible, Metal-Free Hydrogen Activation
Although reversible covalent activation of molecular hydrogen (H₂) is a common reaction at transition metal centers, it has proven elusive in compounds of the lighter elements. We report that the compound (C₆H₂Me₃)₂PH(C₆F₄)BH(C₆F₅)₂ (Me, methyl), which we derived through an unusual reaction involvin...
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| Veröffentlicht in: | Science (American Association for the Advancement of Science) 2006-11, Vol.314 (5802), p.1124-1126 |
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| creator | Welch, Gregory C. San Juan, Ronan R. Masuda, Jason D. Stephan, Douglas W. |
| description | Although reversible covalent activation of molecular hydrogen (H₂) is a common reaction at transition metal centers, it has proven elusive in compounds of the lighter elements. We report that the compound (C₆H₂Me₃)₂PH(C₆F₄)BH(C₆F₅)₂ (Me, methyl), which we derived through an unusual reaction involving dimesitylphosphine substitution at a para carbon of tris(pentafluorophenyl) borane, cleanly loses H₂ at temperatures above 100°C. Preliminary kinetic studies reveal this process to be first order. Remarkably, the dehydrogenated product (C₆H₂Me₃)₂P(C₆F₄)B(C₆F₅)₂ is stable and reacts with 1 atmosphere of H₂ at 25°C to reform the starting complex. Deuteration studies were also carried out to probe the mechanism. |
| doi_str_mv | 10.1126/science.1134230 |
| format | Article |
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We report that the compound (C₆H₂Me₃)₂PH(C₆F₄)BH(C₆F₅)₂ (Me, methyl), which we derived through an unusual reaction involving dimesitylphosphine substitution at a para carbon of tris(pentafluorophenyl) borane, cleanly loses H₂ at temperatures above 100°C. Preliminary kinetic studies reveal this process to be first order. Remarkably, the dehydrogenated product (C₆H₂Me₃)₂P(C₆F₄)B(C₆F₅)₂ is stable and reacts with 1 atmosphere of H₂ at 25°C to reform the starting complex. Deuteration studies were also carried out to probe the mechanism.</description><identifier>ISSN: 0036-8075</identifier><identifier>EISSN: 1095-9203</identifier><identifier>DOI: 10.1126/science.1134230</identifier><identifier>PMID: 17110572</identifier><identifier>CODEN: SCIEAS</identifier><language>eng</language><publisher>Washington, DC: American Association for the Advancement of Science</publisher><subject>Activation ; Adducts ; Alternative fuels. Production and utilization ; Applied sciences ; Boranes ; Carbon ; Catalysis ; Chemical compounds ; Chemical reactions ; Chemistry ; Cleaning ; Colors ; Covalence ; Dehydrogenation ; Energy ; Exact sciences and technology ; Fuels ; General and physical chemistry ; Hydrides ; Hydrogen ; Hydrogen storage ; Kinetics ; Nuclear magnetic resonance ; Phosphines ; Protons ; Temperature ; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry ; Transition metals</subject><ispartof>Science (American Association for the Advancement of Science), 2006-11, Vol.314 (5802), p.1124-1126</ispartof><rights>Copyright 2006 American Association for the Advancement of Science</rights><rights>2007 INIST-CNRS</rights><rights>Copyright American Association for the Advancement of Science Nov 17, 2006</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c535t-f34a22de2bfc0ce1f4ef2e86231e43778cae41b84713237b12e77711cbd91833</citedby><cites>FETCH-LOGICAL-c535t-f34a22de2bfc0ce1f4ef2e86231e43778cae41b84713237b12e77711cbd91833</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.jstor.org/stable/pdf/20032834$$EPDF$$P50$$Gjstor$$H</linktopdf><linktohtml>$$Uhttps://www.jstor.org/stable/20032834$$EHTML$$P50$$Gjstor$$H</linktohtml><link.rule.ids>314,776,780,799,2871,2872,27901,27902,57992,58225</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=18294609$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/17110572$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Welch, Gregory C.</creatorcontrib><creatorcontrib>San Juan, Ronan R.</creatorcontrib><creatorcontrib>Masuda, Jason D.</creatorcontrib><creatorcontrib>Stephan, Douglas W.</creatorcontrib><title>Reversible, Metal-Free Hydrogen Activation</title><title>Science (American Association for the Advancement of Science)</title><addtitle>Science</addtitle><description>Although reversible covalent activation of molecular hydrogen (H₂) is a common reaction at transition metal centers, it has proven elusive in compounds of the lighter elements. We report that the compound (C₆H₂Me₃)₂PH(C₆F₄)BH(C₆F₅)₂ (Me, methyl), which we derived through an unusual reaction involving dimesitylphosphine substitution at a para carbon of tris(pentafluorophenyl) borane, cleanly loses H₂ at temperatures above 100°C. Preliminary kinetic studies reveal this process to be first order. Remarkably, the dehydrogenated product (C₆H₂Me₃)₂P(C₆F₄)B(C₆F₅)₂ is stable and reacts with 1 atmosphere of H₂ at 25°C to reform the starting complex. Deuteration studies were also carried out to probe the mechanism.</description><subject>Activation</subject><subject>Adducts</subject><subject>Alternative fuels. Production and utilization</subject><subject>Applied sciences</subject><subject>Boranes</subject><subject>Carbon</subject><subject>Catalysis</subject><subject>Chemical compounds</subject><subject>Chemical reactions</subject><subject>Chemistry</subject><subject>Cleaning</subject><subject>Colors</subject><subject>Covalence</subject><subject>Dehydrogenation</subject><subject>Energy</subject><subject>Exact sciences and technology</subject><subject>Fuels</subject><subject>General and physical chemistry</subject><subject>Hydrides</subject><subject>Hydrogen</subject><subject>Hydrogen storage</subject><subject>Kinetics</subject><subject>Nuclear magnetic resonance</subject><subject>Phosphines</subject><subject>Protons</subject><subject>Temperature</subject><subject>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</subject><subject>Transition metals</subject><issn>0036-8075</issn><issn>1095-9203</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2006</creationdate><recordtype>article</recordtype><recordid>eNqF0dFL5DAQBvAgHrqnPvukLMLJcVjNzCRN-iii54GHIL6XNDuVLt1Wk-6C_71Ztij4oE8hzC8fGT4hDkGeA2B-EX3Dned0IYUkt8QEZKGzAiVti4mUlGdWGr0rfsY4lzLNCtoRu2AApDY4EX8eeMUhNlXLZ9P_PLg2uwnM09vXWeifuJte-qFZuaHpu33xo3Zt5IPx3BOPN9ePV7fZ3f3ff1eXd5nXpIesJuUQZ4xV7aVnqBXXyDZHAlZkjPWOFVRWGSAkUwGyMek_vpoVYIn2xOkm9jn0L0uOQ7looue2dR33y1jmFnKwGr6FlKPUJNeJv7-EIC2CVYU1iZ58ovN-Gbq0bolAulBartHFBvnQxxi4Lp9Ds3DhNSWV61rKsZZyrCW9OB5jl9WCZx9-7CGBXyNw0bu2Dq7zTfxwFguVyyK5o42bx6EP73NMTaMlRW8Ap5yx</recordid><startdate>20061117</startdate><enddate>20061117</enddate><creator>Welch, Gregory C.</creator><creator>San Juan, Ronan R.</creator><creator>Masuda, Jason D.</creator><creator>Stephan, Douglas W.</creator><general>American Association for the Advancement of Science</general><general>The American Association for the Advancement of Science</general><scope>IQODW</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QF</scope><scope>7QG</scope><scope>7QL</scope><scope>7QP</scope><scope>7QQ</scope><scope>7QR</scope><scope>7SC</scope><scope>7SE</scope><scope>7SN</scope><scope>7SP</scope><scope>7SR</scope><scope>7SS</scope><scope>7T7</scope><scope>7TA</scope><scope>7TB</scope><scope>7TK</scope><scope>7TM</scope><scope>7U5</scope><scope>7U9</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>F28</scope><scope>FR3</scope><scope>H8D</scope><scope>H8G</scope><scope>H94</scope><scope>JG9</scope><scope>JQ2</scope><scope>K9.</scope><scope>KR7</scope><scope>L7M</scope><scope>L~C</scope><scope>L~D</scope><scope>M7N</scope><scope>P64</scope><scope>RC3</scope><scope>7X8</scope></search><sort><creationdate>20061117</creationdate><title>Reversible, Metal-Free Hydrogen Activation</title><author>Welch, Gregory C. ; San Juan, Ronan R. ; Masuda, Jason D. ; Stephan, Douglas W.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c535t-f34a22de2bfc0ce1f4ef2e86231e43778cae41b84713237b12e77711cbd91833</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2006</creationdate><topic>Activation</topic><topic>Adducts</topic><topic>Alternative fuels. Production and utilization</topic><topic>Applied sciences</topic><topic>Boranes</topic><topic>Carbon</topic><topic>Catalysis</topic><topic>Chemical compounds</topic><topic>Chemical reactions</topic><topic>Chemistry</topic><topic>Cleaning</topic><topic>Colors</topic><topic>Covalence</topic><topic>Dehydrogenation</topic><topic>Energy</topic><topic>Exact sciences and technology</topic><topic>Fuels</topic><topic>General and physical chemistry</topic><topic>Hydrides</topic><topic>Hydrogen</topic><topic>Hydrogen storage</topic><topic>Kinetics</topic><topic>Nuclear magnetic resonance</topic><topic>Phosphines</topic><topic>Protons</topic><topic>Temperature</topic><topic>Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry</topic><topic>Transition metals</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Welch, Gregory C.</creatorcontrib><creatorcontrib>San Juan, Ronan R.</creatorcontrib><creatorcontrib>Masuda, Jason D.</creatorcontrib><creatorcontrib>Stephan, Douglas W.</creatorcontrib><collection>Pascal-Francis</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Aluminium Industry Abstracts</collection><collection>Animal Behavior Abstracts</collection><collection>Bacteriology Abstracts (Microbiology B)</collection><collection>Calcium & Calcified Tissue Abstracts</collection><collection>Ceramic Abstracts</collection><collection>Chemoreception Abstracts</collection><collection>Computer and Information Systems Abstracts</collection><collection>Corrosion Abstracts</collection><collection>Ecology Abstracts</collection><collection>Electronics & Communications Abstracts</collection><collection>Engineered Materials Abstracts</collection><collection>Entomology Abstracts (Full archive)</collection><collection>Industrial and Applied Microbiology Abstracts (Microbiology A)</collection><collection>Materials Business File</collection><collection>Mechanical & Transportation Engineering Abstracts</collection><collection>Neurosciences Abstracts</collection><collection>Nucleic Acids Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Virology and AIDS Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>ANTE: Abstracts in New Technology & Engineering</collection><collection>Engineering Research Database</collection><collection>Aerospace Database</collection><collection>Copper Technical Reference Library</collection><collection>AIDS and Cancer Research Abstracts</collection><collection>Materials Research Database</collection><collection>ProQuest Computer Science Collection</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>Civil Engineering Abstracts</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>Computer and Information Systems Abstracts Academic</collection><collection>Computer and Information Systems Abstracts Professional</collection><collection>Algology Mycology and Protozoology Abstracts (Microbiology C)</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>Genetics Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Science (American Association for the Advancement of Science)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Welch, Gregory C.</au><au>San Juan, Ronan R.</au><au>Masuda, Jason D.</au><au>Stephan, Douglas W.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reversible, Metal-Free Hydrogen Activation</atitle><jtitle>Science (American Association for the Advancement of Science)</jtitle><addtitle>Science</addtitle><date>2006-11-17</date><risdate>2006</risdate><volume>314</volume><issue>5802</issue><spage>1124</spage><epage>1126</epage><pages>1124-1126</pages><issn>0036-8075</issn><eissn>1095-9203</eissn><coden>SCIEAS</coden><abstract>Although reversible covalent activation of molecular hydrogen (H₂) is a common reaction at transition metal centers, it has proven elusive in compounds of the lighter elements. We report that the compound (C₆H₂Me₃)₂PH(C₆F₄)BH(C₆F₅)₂ (Me, methyl), which we derived through an unusual reaction involving dimesitylphosphine substitution at a para carbon of tris(pentafluorophenyl) borane, cleanly loses H₂ at temperatures above 100°C. Preliminary kinetic studies reveal this process to be first order. Remarkably, the dehydrogenated product (C₆H₂Me₃)₂P(C₆F₄)B(C₆F₅)₂ is stable and reacts with 1 atmosphere of H₂ at 25°C to reform the starting complex. Deuteration studies were also carried out to probe the mechanism.</abstract><cop>Washington, DC</cop><pub>American Association for the Advancement of Science</pub><pmid>17110572</pmid><doi>10.1126/science.1134230</doi><tpages>3</tpages></addata></record> |
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| subjects | Activation Adducts Alternative fuels. Production and utilization Applied sciences Boranes Carbon Catalysis Chemical compounds Chemical reactions Chemistry Cleaning Colors Covalence Dehydrogenation Energy Exact sciences and technology Fuels General and physical chemistry Hydrides Hydrogen Hydrogen storage Kinetics Nuclear magnetic resonance Phosphines Protons Temperature Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry Transition metals |
| title | Reversible, Metal-Free Hydrogen Activation |
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