Homolytic Cleavage of a B−B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification
Density functional theory (DFT) investigations revealed that 4‐cyanopyridine was capable of homolytically cleaving the B−B σ bond of diborane via the cooperative coordination to the two boron atoms of the diborane to generate pyridine boryl radicals. Our experimental verification provides supportive...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2016-05, Vol.55 (20), p.5985-5989 |
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| creator | Wang, Guoqiang Zhang, Honglin Zhao, Jiyang Li, Wei Cao, Jia Zhu, Chengjian Li, Shuhua |
| description | Density functional theory (DFT) investigations revealed that 4‐cyanopyridine was capable of homolytically cleaving the B−B σ bond of diborane via the cooperative coordination to the two boron atoms of the diborane to generate pyridine boryl radicals. Our experimental verification provides supportive evidence for this new B−B activation mode. With this novel activation strategy, we have experimentally realized the catalytic reduction of azo‐compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones with B2(pin)2 at mild conditions.
Breaking good: The diborane B−B bond can be homolytically cleaved via the cooperative catalysis of two 4‐cyanopyridine molecules. Using this combination of a diborane (B2(pin)2) and 4‐cyanopyridine also allows the catalytic reduction of the N=N double bond of azo‐compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones under mild conditions. |
| doi_str_mv | 10.1002/anie.201511917 |
| format | Article |
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Breaking good: The diborane B−B bond can be homolytically cleaved via the cooperative catalysis of two 4‐cyanopyridine molecules. Using this combination of a diborane (B2(pin)2) and 4‐cyanopyridine also allows the catalytic reduction of the N=N double bond of azo‐compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones under mild conditions.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201511917</identifier><identifier>PMID: 27061603</identifier><identifier>CODEN: ACIEAY</identifier><language>eng</language><publisher>Germany: Blackwell Publishing Ltd</publisher><subject>Activation ; Boron ; B−B bond activation ; Catalysis ; Chemical reduction ; computational design ; Computer applications ; cooperative activation ; Density functional theory ; Deoxygenation ; Diborane ; homolytic cleavage ; Hydrazine ; Hydrazines ; Lewis base ; Program verification (computers) ; Pyridines ; Quinones</subject><ispartof>Angewandte Chemie International Edition, 2016-05, Vol.55 (20), p.5985-5989</ispartof><rights>2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><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-c5427-70d7e58d125467d572a7460d790020aabf20fbda1d17121c123ce8eb8e5cc4353</citedby><cites>FETCH-LOGICAL-c5427-70d7e58d125467d572a7460d790020aabf20fbda1d17121c123ce8eb8e5cc4353</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.201511917$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201511917$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/27061603$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Wang, Guoqiang</creatorcontrib><creatorcontrib>Zhang, Honglin</creatorcontrib><creatorcontrib>Zhao, Jiyang</creatorcontrib><creatorcontrib>Li, Wei</creatorcontrib><creatorcontrib>Cao, Jia</creatorcontrib><creatorcontrib>Zhu, Chengjian</creatorcontrib><creatorcontrib>Li, Shuhua</creatorcontrib><title>Homolytic Cleavage of a B−B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification</title><title>Angewandte Chemie International Edition</title><addtitle>Angew. Chem. Int. Ed</addtitle><description>Density functional theory (DFT) investigations revealed that 4‐cyanopyridine was capable of homolytically cleaving the B−B σ bond of diborane via the cooperative coordination to the two boron atoms of the diborane to generate pyridine boryl radicals. Our experimental verification provides supportive evidence for this new B−B activation mode. With this novel activation strategy, we have experimentally realized the catalytic reduction of azo‐compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones with B2(pin)2 at mild conditions.
Breaking good: The diborane B−B bond can be homolytically cleaved via the cooperative catalysis of two 4‐cyanopyridine molecules. Using this combination of a diborane (B2(pin)2) and 4‐cyanopyridine also allows the catalytic reduction of the N=N double bond of azo‐compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones under mild conditions.</description><subject>Activation</subject><subject>Boron</subject><subject>B−B bond activation</subject><subject>Catalysis</subject><subject>Chemical reduction</subject><subject>computational design</subject><subject>Computer applications</subject><subject>cooperative activation</subject><subject>Density functional theory</subject><subject>Deoxygenation</subject><subject>Diborane</subject><subject>homolytic cleavage</subject><subject>Hydrazine</subject><subject>Hydrazines</subject><subject>Lewis base</subject><subject>Program verification (computers)</subject><subject>Pyridines</subject><subject>Quinones</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqFkcFu1DAQhiMEoqVw5YgsceGSxePEccKtCdttpaVcSnu0nGRSXJJ4Gyfd7gsgzjwiT8IsW1aIA5w8tr7_k8Z_ELwEPgPOxVvTW5wJDhIgA_UoOAQpIIyUih7THEdRqFIJB8Ez72-IT1OePA0OhOIJJDw6DL6eus61m9FWrGjR3JlrZK5hhuU_vn3PWe76mpUbNn5GVji3wsGM9o5mM5p2463fwhdrx5a4pktuPPp3RHaraSTS9aZl79Hb654ZMs3vyWA77CnNLmlsbPULex48aUzr8cXDeRR8OplfFKfh8uPirDhehpWMhQoVrxXKtAYh40TVUgmj4oQeM9qNG1M2gjdlbaAGBQIqEFGFKZYpyqqKIxkdBW923tXgbif0o-6sr7BtTY9u8hpUqnjGU6EIff0XeuOmgRbyWnCp6PcTnv2LIlciJOeQEjXbUdXgvB-w0Sv6BjNsNHC97VFve9T7Hinw6kE7lR3We_x3cQRkO2BtW9z8R6ePz8_mf8rDXdb6Ee_3WTN80YmKlNRX5wv94Qoui_gk14voJ1vBuEM</recordid><startdate>20160510</startdate><enddate>20160510</enddate><creator>Wang, Guoqiang</creator><creator>Zhang, Honglin</creator><creator>Zhao, Jiyang</creator><creator>Li, Wei</creator><creator>Cao, Jia</creator><creator>Zhu, Chengjian</creator><creator>Li, Shuhua</creator><general>Blackwell Publishing Ltd</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope></search><sort><creationdate>20160510</creationdate><title>Homolytic Cleavage of a B−B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification</title><author>Wang, Guoqiang ; Zhang, Honglin ; Zhao, Jiyang ; Li, Wei ; Cao, Jia ; Zhu, Chengjian ; Li, Shuhua</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5427-70d7e58d125467d572a7460d790020aabf20fbda1d17121c123ce8eb8e5cc4353</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Activation</topic><topic>Boron</topic><topic>B−B bond activation</topic><topic>Catalysis</topic><topic>Chemical reduction</topic><topic>computational design</topic><topic>Computer applications</topic><topic>cooperative activation</topic><topic>Density functional theory</topic><topic>Deoxygenation</topic><topic>Diborane</topic><topic>homolytic cleavage</topic><topic>Hydrazine</topic><topic>Hydrazines</topic><topic>Lewis base</topic><topic>Program verification (computers)</topic><topic>Pyridines</topic><topic>Quinones</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Wang, Guoqiang</creatorcontrib><creatorcontrib>Zhang, Honglin</creatorcontrib><creatorcontrib>Zhao, Jiyang</creatorcontrib><creatorcontrib>Li, Wei</creatorcontrib><creatorcontrib>Cao, Jia</creatorcontrib><creatorcontrib>Zhu, Chengjian</creatorcontrib><creatorcontrib>Li, Shuhua</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Wang, Guoqiang</au><au>Zhang, Honglin</au><au>Zhao, Jiyang</au><au>Li, Wei</au><au>Cao, Jia</au><au>Zhu, Chengjian</au><au>Li, Shuhua</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Homolytic Cleavage of a B−B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2016-05-10</date><risdate>2016</risdate><volume>55</volume><issue>20</issue><spage>5985</spage><epage>5989</epage><pages>5985-5989</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><coden>ACIEAY</coden><abstract>Density functional theory (DFT) investigations revealed that 4‐cyanopyridine was capable of homolytically cleaving the B−B σ bond of diborane via the cooperative coordination to the two boron atoms of the diborane to generate pyridine boryl radicals. Our experimental verification provides supportive evidence for this new B−B activation mode. With this novel activation strategy, we have experimentally realized the catalytic reduction of azo‐compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones with B2(pin)2 at mild conditions.
Breaking good: The diborane B−B bond can be homolytically cleaved via the cooperative catalysis of two 4‐cyanopyridine molecules. Using this combination of a diborane (B2(pin)2) and 4‐cyanopyridine also allows the catalytic reduction of the N=N double bond of azo‐compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones under mild conditions.</abstract><cop>Germany</cop><pub>Blackwell Publishing Ltd</pub><pmid>27061603</pmid><doi>10.1002/anie.201511917</doi><tpages>5</tpages><edition>International ed. in English</edition></addata></record> |
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| subjects | Activation Boron B−B bond activation Catalysis Chemical reduction computational design Computer applications cooperative activation Density functional theory Deoxygenation Diborane homolytic cleavage Hydrazine Hydrazines Lewis base Program verification (computers) Pyridines Quinones |
| title | Homolytic Cleavage of a B−B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification |
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