A Potassium Diboryllithate: Synthesis, Bonding Properties, and the Deprotonation of Benzene
A potassium diboryllithate (B2LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B2LiK, revealed ionic interactions between the two bridging boryl anions and Li+ and K+. Upon standing in benzene, B2LiK deprotonated the solvent to form a hydrobora...
Gespeichert in:
| Veröffentlicht in: | Angewandte Chemie International Edition 2016-09, Vol.55 (38), p.11426-11430 |
|---|---|
| Hauptverfasser: | , , , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 11430 |
|---|---|
| container_issue | 38 |
| container_start_page | 11426 |
| container_title | Angewandte Chemie International Edition |
| container_volume | 55 |
| creator | Ohsato, Takuto Okuno, Yuri Ishida, Shintaro Iwamoto, Takeaki Lee, Ka-Ho Lin, Zhenyang Yamashita, Makoto Nozaki, Kyoko |
| description | A potassium diboryllithate (B2LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B2LiK, revealed ionic interactions between the two bridging boryl anions and Li+ and K+. Upon standing in benzene, B2LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K+.
A ’LiK ’ of work: A potassium diboryllithate, B2LiK, was synthesized and structurally characterized. The bonding situation in this compound was examined by NMR, XRD, NPA, and AIM analyses. B2LiK is able to deprotonate benzene with concomitant formation of phenylborane as the major product. A detailed reaction mechanism based on DFT calculations suggests that the deprotonation of benzene should be initiated by a transition state involving the coordination of benzene to K+. |
| doi_str_mv | 10.1002/anie.201605005 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1817560010</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>4171180411</sourcerecordid><originalsourceid>FETCH-LOGICAL-c5825-72a009d7548275b497e19ffc891c1c099da6343e4e1c278c916986d180462f223</originalsourceid><addsrcrecordid>eNqFkUtvEzEUhS0Eog_YskSW2LDopH6Mxza7NC2lIiqpKGLBwnJm7lCXiR1sjyD8elylRBULWPnK_s7xuToIvaBkQglhx9Y7mDBCGyIIEY_QPhWMVlxK_rjMNeeVVILuoYOUbguvFGmeoj0mBedE6330ZYoXIduU3LjCp24Z4mYYXL6xGd7gjxufbyC5dIRPgu-c_4oXMawhZgflzvoOl3d8CusYcvA2u-Bx6PEJ-F_g4Rl60tshwfP78xB9ent2PXtXzT-cX8ym86oViolKMkuI7qSoVcm1rLUEqvu-VZq2tC0pO9vwmkMNtGVStZo2WjUdVaRuWM8YP0Svt74lxvcRUjYrl1oYBushjMlQRaVoCKGkoK_-Qm_DGH1JZ6gm5f-aNvKflCqAVpLUhZpsqTaGlCL0Zh3dysaNocTclWPuyjG7corg5b3tuFxBt8P_tFEAvQV-uAE2_7Ez08uLs4fm1VbrUoafO62N30zZSArz-fLcXL1fyKvrGTdz_htGL6eH</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1816798704</pqid></control><display><type>article</type><title>A Potassium Diboryllithate: Synthesis, Bonding Properties, and the Deprotonation of Benzene</title><source>Access via Wiley Online Library</source><creator>Ohsato, Takuto ; Okuno, Yuri ; Ishida, Shintaro ; Iwamoto, Takeaki ; Lee, Ka-Ho ; Lin, Zhenyang ; Yamashita, Makoto ; Nozaki, Kyoko</creator><creatorcontrib>Ohsato, Takuto ; Okuno, Yuri ; Ishida, Shintaro ; Iwamoto, Takeaki ; Lee, Ka-Ho ; Lin, Zhenyang ; Yamashita, Makoto ; Nozaki, Kyoko</creatorcontrib><description>A potassium diboryllithate (B2LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B2LiK, revealed ionic interactions between the two bridging boryl anions and Li+ and K+. Upon standing in benzene, B2LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K+.
A ’LiK ’ of work: A potassium diboryllithate, B2LiK, was synthesized and structurally characterized. The bonding situation in this compound was examined by NMR, XRD, NPA, and AIM analyses. B2LiK is able to deprotonate benzene with concomitant formation of phenylborane as the major product. A detailed reaction mechanism based on DFT calculations suggests that the deprotonation of benzene should be initiated by a transition state involving the coordination of benzene to K+.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201605005</identifier><identifier>PMID: 27533099</identifier><identifier>CODEN: ACIEAY</identifier><language>eng</language><publisher>Germany: Blackwell Publishing Ltd</publisher><subject>Anions ; Benzene ; Bonding ; boron ; Bridging ; computational chemistry ; Hydrocarbons ; Ion exchange ; Ionic interactions ; Mathematical analysis ; Potassium ; structure determination ; superbases</subject><ispartof>Angewandte Chemie International Edition, 2016-09, Vol.55 (38), p.11426-11430</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><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5825-72a009d7548275b497e19ffc891c1c099da6343e4e1c278c916986d180462f223</citedby><cites>FETCH-LOGICAL-c5825-72a009d7548275b497e19ffc891c1c099da6343e4e1c278c916986d180462f223</cites><orcidid>0000-0002-3665-5311</orcidid></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.201605005$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201605005$$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/27533099$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Ohsato, Takuto</creatorcontrib><creatorcontrib>Okuno, Yuri</creatorcontrib><creatorcontrib>Ishida, Shintaro</creatorcontrib><creatorcontrib>Iwamoto, Takeaki</creatorcontrib><creatorcontrib>Lee, Ka-Ho</creatorcontrib><creatorcontrib>Lin, Zhenyang</creatorcontrib><creatorcontrib>Yamashita, Makoto</creatorcontrib><creatorcontrib>Nozaki, Kyoko</creatorcontrib><title>A Potassium Diboryllithate: Synthesis, Bonding Properties, and the Deprotonation of Benzene</title><title>Angewandte Chemie International Edition</title><addtitle>Angew. Chem. Int. Ed</addtitle><description>A potassium diboryllithate (B2LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B2LiK, revealed ionic interactions between the two bridging boryl anions and Li+ and K+. Upon standing in benzene, B2LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K+.
A ’LiK ’ of work: A potassium diboryllithate, B2LiK, was synthesized and structurally characterized. The bonding situation in this compound was examined by NMR, XRD, NPA, and AIM analyses. B2LiK is able to deprotonate benzene with concomitant formation of phenylborane as the major product. A detailed reaction mechanism based on DFT calculations suggests that the deprotonation of benzene should be initiated by a transition state involving the coordination of benzene to K+.</description><subject>Anions</subject><subject>Benzene</subject><subject>Bonding</subject><subject>boron</subject><subject>Bridging</subject><subject>computational chemistry</subject><subject>Hydrocarbons</subject><subject>Ion exchange</subject><subject>Ionic interactions</subject><subject>Mathematical analysis</subject><subject>Potassium</subject><subject>structure determination</subject><subject>superbases</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqFkUtvEzEUhS0Eog_YskSW2LDopH6Mxza7NC2lIiqpKGLBwnJm7lCXiR1sjyD8elylRBULWPnK_s7xuToIvaBkQglhx9Y7mDBCGyIIEY_QPhWMVlxK_rjMNeeVVILuoYOUbguvFGmeoj0mBedE6330ZYoXIduU3LjCp24Z4mYYXL6xGd7gjxufbyC5dIRPgu-c_4oXMawhZgflzvoOl3d8CusYcvA2u-Bx6PEJ-F_g4Rl60tshwfP78xB9ent2PXtXzT-cX8ym86oViolKMkuI7qSoVcm1rLUEqvu-VZq2tC0pO9vwmkMNtGVStZo2WjUdVaRuWM8YP0Svt74lxvcRUjYrl1oYBushjMlQRaVoCKGkoK_-Qm_DGH1JZ6gm5f-aNvKflCqAVpLUhZpsqTaGlCL0Zh3dysaNocTclWPuyjG7corg5b3tuFxBt8P_tFEAvQV-uAE2_7Ez08uLs4fm1VbrUoafO62N30zZSArz-fLcXL1fyKvrGTdz_htGL6eH</recordid><startdate>20160912</startdate><enddate>20160912</enddate><creator>Ohsato, Takuto</creator><creator>Okuno, Yuri</creator><creator>Ishida, Shintaro</creator><creator>Iwamoto, Takeaki</creator><creator>Lee, Ka-Ho</creator><creator>Lin, Zhenyang</creator><creator>Yamashita, Makoto</creator><creator>Nozaki, Kyoko</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><orcidid>https://orcid.org/0000-0002-3665-5311</orcidid></search><sort><creationdate>20160912</creationdate><title>A Potassium Diboryllithate: Synthesis, Bonding Properties, and the Deprotonation of Benzene</title><author>Ohsato, Takuto ; Okuno, Yuri ; Ishida, Shintaro ; Iwamoto, Takeaki ; Lee, Ka-Ho ; Lin, Zhenyang ; Yamashita, Makoto ; Nozaki, Kyoko</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5825-72a009d7548275b497e19ffc891c1c099da6343e4e1c278c916986d180462f223</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Anions</topic><topic>Benzene</topic><topic>Bonding</topic><topic>boron</topic><topic>Bridging</topic><topic>computational chemistry</topic><topic>Hydrocarbons</topic><topic>Ion exchange</topic><topic>Ionic interactions</topic><topic>Mathematical analysis</topic><topic>Potassium</topic><topic>structure determination</topic><topic>superbases</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ohsato, Takuto</creatorcontrib><creatorcontrib>Okuno, Yuri</creatorcontrib><creatorcontrib>Ishida, Shintaro</creatorcontrib><creatorcontrib>Iwamoto, Takeaki</creatorcontrib><creatorcontrib>Lee, Ka-Ho</creatorcontrib><creatorcontrib>Lin, Zhenyang</creatorcontrib><creatorcontrib>Yamashita, Makoto</creatorcontrib><creatorcontrib>Nozaki, Kyoko</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>Ohsato, Takuto</au><au>Okuno, Yuri</au><au>Ishida, Shintaro</au><au>Iwamoto, Takeaki</au><au>Lee, Ka-Ho</au><au>Lin, Zhenyang</au><au>Yamashita, Makoto</au><au>Nozaki, Kyoko</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Potassium Diboryllithate: Synthesis, Bonding Properties, and the Deprotonation of Benzene</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2016-09-12</date><risdate>2016</risdate><volume>55</volume><issue>38</issue><spage>11426</spage><epage>11430</epage><pages>11426-11430</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><coden>ACIEAY</coden><abstract>A potassium diboryllithate (B2LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B2LiK, revealed ionic interactions between the two bridging boryl anions and Li+ and K+. Upon standing in benzene, B2LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K+.
A ’LiK ’ of work: A potassium diboryllithate, B2LiK, was synthesized and structurally characterized. The bonding situation in this compound was examined by NMR, XRD, NPA, and AIM analyses. B2LiK is able to deprotonate benzene with concomitant formation of phenylborane as the major product. A detailed reaction mechanism based on DFT calculations suggests that the deprotonation of benzene should be initiated by a transition state involving the coordination of benzene to K+.</abstract><cop>Germany</cop><pub>Blackwell Publishing Ltd</pub><pmid>27533099</pmid><doi>10.1002/anie.201605005</doi><tpages>5</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0002-3665-5311</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1433-7851 |
| ispartof | Angewandte Chemie International Edition, 2016-09, Vol.55 (38), p.11426-11430 |
| issn | 1433-7851 1521-3773 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_1817560010 |
| source | Access via Wiley Online Library |
| subjects | Anions Benzene Bonding boron Bridging computational chemistry Hydrocarbons Ion exchange Ionic interactions Mathematical analysis Potassium structure determination superbases |
| title | A Potassium Diboryllithate: Synthesis, Bonding Properties, and the Deprotonation of Benzene |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-25T10%3A15%3A07IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=A%20Potassium%20Diboryllithate:%20Synthesis,%20Bonding%20Properties,%20and%20the%20Deprotonation%20of%20Benzene&rft.jtitle=Angewandte%20Chemie%20International%20Edition&rft.au=Ohsato,%20Takuto&rft.date=2016-09-12&rft.volume=55&rft.issue=38&rft.spage=11426&rft.epage=11430&rft.pages=11426-11430&rft.issn=1433-7851&rft.eissn=1521-3773&rft.coden=ACIEAY&rft_id=info:doi/10.1002/anie.201605005&rft_dat=%3Cproquest_cross%3E4171180411%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=1816798704&rft_id=info:pmid/27533099&rfr_iscdi=true |