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Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols
The oxidation of alcohols with N2O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin)amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N2...
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Published in: | Angewandte Chemie 2016-01, Vol.128 (5), p.1886-1890 |
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container_end_page | 1890 |
container_issue | 5 |
container_start_page | 1886 |
container_title | Angewandte Chemie |
container_volume | 128 |
creator | Gianetti, Thomas L. Annen, Samuel P. Santiso-Quinones, Gustavo Reiher, Markus Driess, Matthias Grützmacher, Hansjörg |
description | The oxidation of alcohols with N2O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin)amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N2 and water are the only by‐products. Mechanistic studies supported by DFT calculations suggest that the oxygen atom of N2O is transferred to the metal center by insertion into the Rh−H bond of a rhodium amino hydride species, generating a rhodium hydroxy complex as a key intermediate.
Wird N2O als Wasserstoffakzeptor in der dehydrierenden Kupplung primärer Alkohole eingesetzt, werden als einzige Beiprodukte N2 und H2O gebildet. Diese Reaktion, die von einem Bis(olefin)amin‐Rhodium(I)‐Komplex unter milden Bedingungen katalysiert wird, zeichnet sich durch eine große Substratbreite aus. |
doi_str_mv | 10.1002/ange.201509288 |
format | article |
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Wird N2O als Wasserstoffakzeptor in der dehydrierenden Kupplung primärer Alkohole eingesetzt, werden als einzige Beiprodukte N2 und H2O gebildet. Diese Reaktion, die von einem Bis(olefin)amin‐Rhodium(I)‐Komplex unter milden Bedingungen katalysiert wird, zeichnet sich durch eine große Substratbreite aus.</description><identifier>ISSN: 0044-8249</identifier><identifier>EISSN: 1521-3757</identifier><identifier>DOI: 10.1002/ange.201509288</identifier><language>eng ; ger</language><publisher>Weinheim: Blackwell Publishing Ltd</publisher><subject>Alcohol ; Alcohols ; Alkohole ; Byproducts ; Catalysts ; Chemistry ; Coupling ; Dehydrierungen ; Dehydrogenation ; Distickstoffoxid ; Esters ; Hydrogen ; Hydrogen storage ; Insertion ; Katalyse ; Kupplungsreaktionen ; Ligands ; Mathematical analysis ; Metals ; Nitrous oxide ; Nitrous oxides ; Oxidation ; Oxygen ; Rhodium</subject><ispartof>Angewandte Chemie, 2016-01, Vol.128 (5), p.1886-1890</ispartof><rights>2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c2618-5f0a9bc98f5608fe0b8a13c539370352f658eeb73437643c3dfc2881c95ddbfc3</citedby><cites>FETCH-LOGICAL-c2618-5f0a9bc98f5608fe0b8a13c539370352f658eeb73437643c3dfc2881c95ddbfc3</cites><orcidid>0000-0002-1531-8906</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Gianetti, Thomas L.</creatorcontrib><creatorcontrib>Annen, Samuel P.</creatorcontrib><creatorcontrib>Santiso-Quinones, Gustavo</creatorcontrib><creatorcontrib>Reiher, Markus</creatorcontrib><creatorcontrib>Driess, Matthias</creatorcontrib><creatorcontrib>Grützmacher, Hansjörg</creatorcontrib><title>Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols</title><title>Angewandte Chemie</title><addtitle>Angew. Chem</addtitle><description>The oxidation of alcohols with N2O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin)amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N2 and water are the only by‐products. Mechanistic studies supported by DFT calculations suggest that the oxygen atom of N2O is transferred to the metal center by insertion into the Rh−H bond of a rhodium amino hydride species, generating a rhodium hydroxy complex as a key intermediate.
Wird N2O als Wasserstoffakzeptor in der dehydrierenden Kupplung primärer Alkohole eingesetzt, werden als einzige Beiprodukte N2 und H2O gebildet. Diese Reaktion, die von einem Bis(olefin)amin‐Rhodium(I)‐Komplex unter milden Bedingungen katalysiert wird, zeichnet sich durch eine große Substratbreite aus.</description><subject>Alcohol</subject><subject>Alcohols</subject><subject>Alkohole</subject><subject>Byproducts</subject><subject>Catalysts</subject><subject>Chemistry</subject><subject>Coupling</subject><subject>Dehydrierungen</subject><subject>Dehydrogenation</subject><subject>Distickstoffoxid</subject><subject>Esters</subject><subject>Hydrogen</subject><subject>Hydrogen storage</subject><subject>Insertion</subject><subject>Katalyse</subject><subject>Kupplungsreaktionen</subject><subject>Ligands</subject><subject>Mathematical analysis</subject><subject>Metals</subject><subject>Nitrous oxide</subject><subject>Nitrous oxides</subject><subject>Oxidation</subject><subject>Oxygen</subject><subject>Rhodium</subject><issn>0044-8249</issn><issn>1521-3757</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqFkU1rGzEURUVpoK7bbdeCbrIZVx-jkbR0bMcuGJtAQroTsubJnmQycqRxGv_7KjiE0kWzEFronMe7ugh9o2RECWE_bLeFESNUEM2U-oAGVDBacCnkRzQgpCwLxUr9CX1O6Y4QUjGpB-hq1fQxHBJePzc1YJuwxYtjHcMWOjx2DvZ9iNjn0-8AT2H3-mb75gnwJBz2bdNtcfB43LqwC236gs68bRN8fb2H6OZydj1ZFMv1_OdkvCwcq6gqhCdWb5xWXlREeSAbZSl3gmsuCRfMV0IBbCQvuaxK7njtXY5FnRZ1vfGOD9H5ae4-hscDpN48NMlB29oOciBDVc6sGeM0o9__Qe_CIXZ5O0N1_hipqRD_paRQFSWKyUyNTpSLIaUI3uxj82Dj0VBiXnowLz2Ytx6yoE_C76aF4zu0Ga_ms7_d4uQ2qYfnN9fGe1PJ3Ky5Xc3NVF1clUvxy1zzP5rImXI</recordid><startdate>20160126</startdate><enddate>20160126</enddate><creator>Gianetti, Thomas L.</creator><creator>Annen, Samuel P.</creator><creator>Santiso-Quinones, Gustavo</creator><creator>Reiher, Markus</creator><creator>Driess, Matthias</creator><creator>Grützmacher, Hansjörg</creator><general>Blackwell Publishing Ltd</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><orcidid>https://orcid.org/0000-0002-1531-8906</orcidid></search><sort><creationdate>20160126</creationdate><title>Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols</title><author>Gianetti, Thomas L. ; Annen, Samuel P. ; Santiso-Quinones, Gustavo ; Reiher, Markus ; Driess, Matthias ; Grützmacher, Hansjörg</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2618-5f0a9bc98f5608fe0b8a13c539370352f658eeb73437643c3dfc2881c95ddbfc3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng ; ger</language><creationdate>2016</creationdate><topic>Alcohol</topic><topic>Alcohols</topic><topic>Alkohole</topic><topic>Byproducts</topic><topic>Catalysts</topic><topic>Chemistry</topic><topic>Coupling</topic><topic>Dehydrierungen</topic><topic>Dehydrogenation</topic><topic>Distickstoffoxid</topic><topic>Esters</topic><topic>Hydrogen</topic><topic>Hydrogen storage</topic><topic>Insertion</topic><topic>Katalyse</topic><topic>Kupplungsreaktionen</topic><topic>Ligands</topic><topic>Mathematical analysis</topic><topic>Metals</topic><topic>Nitrous oxide</topic><topic>Nitrous oxides</topic><topic>Oxidation</topic><topic>Oxygen</topic><topic>Rhodium</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Gianetti, Thomas L.</creatorcontrib><creatorcontrib>Annen, Samuel P.</creatorcontrib><creatorcontrib>Santiso-Quinones, Gustavo</creatorcontrib><creatorcontrib>Reiher, Markus</creatorcontrib><creatorcontrib>Driess, Matthias</creatorcontrib><creatorcontrib>Grützmacher, Hansjörg</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Angewandte Chemie</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Gianetti, Thomas L.</au><au>Annen, Samuel P.</au><au>Santiso-Quinones, Gustavo</au><au>Reiher, Markus</au><au>Driess, Matthias</au><au>Grützmacher, Hansjörg</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols</atitle><jtitle>Angewandte Chemie</jtitle><addtitle>Angew. Chem</addtitle><date>2016-01-26</date><risdate>2016</risdate><volume>128</volume><issue>5</issue><spage>1886</spage><epage>1890</epage><pages>1886-1890</pages><issn>0044-8249</issn><eissn>1521-3757</eissn><abstract>The oxidation of alcohols with N2O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin)amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N2 and water are the only by‐products. Mechanistic studies supported by DFT calculations suggest that the oxygen atom of N2O is transferred to the metal center by insertion into the Rh−H bond of a rhodium amino hydride species, generating a rhodium hydroxy complex as a key intermediate.
Wird N2O als Wasserstoffakzeptor in der dehydrierenden Kupplung primärer Alkohole eingesetzt, werden als einzige Beiprodukte N2 und H2O gebildet. Diese Reaktion, die von einem Bis(olefin)amin‐Rhodium(I)‐Komplex unter milden Bedingungen katalysiert wird, zeichnet sich durch eine große Substratbreite aus.</abstract><cop>Weinheim</cop><pub>Blackwell Publishing Ltd</pub><doi>10.1002/ange.201509288</doi><tpages>5</tpages><orcidid>https://orcid.org/0000-0002-1531-8906</orcidid></addata></record> |
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subjects | Alcohol Alcohols Alkohole Byproducts Catalysts Chemistry Coupling Dehydrierungen Dehydrogenation Distickstoffoxid Esters Hydrogen Hydrogen storage Insertion Katalyse Kupplungsreaktionen Ligands Mathematical analysis Metals Nitrous oxide Nitrous oxides Oxidation Oxygen Rhodium |
title | Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols |
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