A two-coordinate boron cation featuring C–B+–C bonding

Two-coordinate boron cations (R 2 B + ), referred to as borinium ions, are chemical species in which the boron bears only four valence electrons, and that are isoelectronic with hypothetical carbon dications (R 2 C 2+ ). Although lone-pair-donating substituents such as amino groups have enabled the...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Nature chemistry 2014-06, Vol.6 (6), p.498-503
Hauptverfasser: Shoji, Yoshiaki, Tanaka, Naoki, Mikami, Koichiro, Uchiyama, Masanobu, Fukushima, Takanori
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 503
container_issue 6
container_start_page 498
container_title Nature chemistry
container_volume 6
creator Shoji, Yoshiaki
Tanaka, Naoki
Mikami, Koichiro
Uchiyama, Masanobu
Fukushima, Takanori
description Two-coordinate boron cations (R 2 B + ), referred to as borinium ions, are chemical species in which the boron bears only four valence electrons, and that are isoelectronic with hypothetical carbon dications (R 2 C 2+ ). Although lone-pair-donating substituents such as amino groups have enabled the isolation of several borinium ions, diarylated and dialkylated borinium derivatives remain entirely unexplored. Here, we present the synthesis, structure and reactivity of the dimesitylborinium ion, which displays unexpectedly high thermal stability. X-ray crystallography and 11 B NMR spectroscopy, supported by density functional theory calculations, reveal that the borinium ion adopts a linear two-coordinate structure in both the solid state and in solution. The boron centre is stabilized by p π bonding from the mesityl groups and is free from coordination by the counterion or solvent molecules. This diarylborinium ion possesses exceptional Lewis acidity, accepting a pair of electrons from CO 2 to cause an unusual deoxygenation reaction. Borinium ions are two-coordinate boron cations that contain only four valence electrons on boron, and are difficult to isolate without electron donation from adjacent heteroatoms. Now, diarylborinium salts with no lone-pair donation from heteroatoms have been isolated, characterized and found to participate in an unusual reaction with CO 2 .
doi_str_mv 10.1038/nchem.1948
format Article
fullrecord <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1528336840</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1528336840</sourcerecordid><originalsourceid>FETCH-LOGICAL-c461t-6c8ad44553145a7d28c79cd2e41861f1d6e5ffa8e6418e64b54feb9c1e3cf61e3</originalsourceid><addsrcrecordid>eNplkMtKAzEUhoMotlY3PoAMuBHL1GRyacZdHbxBwY2uQyaT1CmdpCYziDvfwTf0SUxtLaKb_4Tw8Z_DB8AxgiMEMb-w6lk3I5QTvgP6aExpSjDJd7dvDHvgIIQ5hIxixPZBLyOc8AzTPricJO2rS5VzvqqtbHVSOu9somRbx2G0bDtf21lSfL5_XA1jFJGwkZ0dgj0jF0EfbeYAPN1cPxZ36fTh9r6YTFNFGGpTprisCKFxNaFyXGVcjXNVZZogzpBBFdPUGMk1ix8xSkqMLnOFNFaGxRyAs3Xv0ruXTodWNHVQerGQVrsuCEQzjjHjBEb09A86d5238TqBGGWQUg5JpM7XlPIuBK-NWPq6kf5NIChWRsW3UbEyGuGTTWVXNrraoj8KIzBcA2G5EqX9r53_674A0SaAZA</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1656055804</pqid></control><display><type>article</type><title>A two-coordinate boron cation featuring C–B+–C bonding</title><source>MEDLINE</source><source>Nature</source><source>Alma/SFX Local Collection</source><creator>Shoji, Yoshiaki ; Tanaka, Naoki ; Mikami, Koichiro ; Uchiyama, Masanobu ; Fukushima, Takanori</creator><creatorcontrib>Shoji, Yoshiaki ; Tanaka, Naoki ; Mikami, Koichiro ; Uchiyama, Masanobu ; Fukushima, Takanori</creatorcontrib><description>Two-coordinate boron cations (R 2 B + ), referred to as borinium ions, are chemical species in which the boron bears only four valence electrons, and that are isoelectronic with hypothetical carbon dications (R 2 C 2+ ). Although lone-pair-donating substituents such as amino groups have enabled the isolation of several borinium ions, diarylated and dialkylated borinium derivatives remain entirely unexplored. Here, we present the synthesis, structure and reactivity of the dimesitylborinium ion, which displays unexpectedly high thermal stability. X-ray crystallography and 11 B NMR spectroscopy, supported by density functional theory calculations, reveal that the borinium ion adopts a linear two-coordinate structure in both the solid state and in solution. The boron centre is stabilized by p π bonding from the mesityl groups and is free from coordination by the counterion or solvent molecules. This diarylborinium ion possesses exceptional Lewis acidity, accepting a pair of electrons from CO 2 to cause an unusual deoxygenation reaction. Borinium ions are two-coordinate boron cations that contain only four valence electrons on boron, and are difficult to isolate without electron donation from adjacent heteroatoms. Now, diarylborinium salts with no lone-pair donation from heteroatoms have been isolated, characterized and found to participate in an unusual reaction with CO 2 .</description><identifier>ISSN: 1755-4330</identifier><identifier>EISSN: 1755-4349</identifier><identifier>DOI: 10.1038/nchem.1948</identifier><identifier>PMID: 24848235</identifier><language>eng</language><publisher>London: Nature Publishing Group UK</publisher><subject>639/638/406/910 ; 639/638/406/911 ; 639/638/549 ; Acidity ; Analytical Chemistry ; Biochemistry ; Boron ; Boron Compounds - chemistry ; Carbon ; Carbon dioxide ; Carbon Dioxide - chemistry ; Cations ; Cations - chemistry ; Chemical bonds ; Chemical speciation ; Chemistry ; Chemistry/Food Science ; Crystallography ; Crystallography, X-Ray ; Inorganic Chemistry ; Ions ; Lewis Acids - chemistry ; Magnetic Resonance Spectroscopy ; Models, Molecular ; Molecular Structure ; Organic Chemistry ; Oxidation-Reduction ; Physical Chemistry ; Solvents ; Spectroscopy</subject><ispartof>Nature chemistry, 2014-06, Vol.6 (6), p.498-503</ispartof><rights>Springer Nature Limited 2014</rights><rights>Copyright Nature Publishing Group Jun 2014</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c461t-6c8ad44553145a7d28c79cd2e41861f1d6e5ffa8e6418e64b54feb9c1e3cf61e3</citedby><cites>FETCH-LOGICAL-c461t-6c8ad44553145a7d28c79cd2e41861f1d6e5ffa8e6418e64b54feb9c1e3cf61e3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,781,785,27929,27930</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/24848235$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Shoji, Yoshiaki</creatorcontrib><creatorcontrib>Tanaka, Naoki</creatorcontrib><creatorcontrib>Mikami, Koichiro</creatorcontrib><creatorcontrib>Uchiyama, Masanobu</creatorcontrib><creatorcontrib>Fukushima, Takanori</creatorcontrib><title>A two-coordinate boron cation featuring C–B+–C bonding</title><title>Nature chemistry</title><addtitle>Nature Chem</addtitle><addtitle>Nat Chem</addtitle><description>Two-coordinate boron cations (R 2 B + ), referred to as borinium ions, are chemical species in which the boron bears only four valence electrons, and that are isoelectronic with hypothetical carbon dications (R 2 C 2+ ). Although lone-pair-donating substituents such as amino groups have enabled the isolation of several borinium ions, diarylated and dialkylated borinium derivatives remain entirely unexplored. Here, we present the synthesis, structure and reactivity of the dimesitylborinium ion, which displays unexpectedly high thermal stability. X-ray crystallography and 11 B NMR spectroscopy, supported by density functional theory calculations, reveal that the borinium ion adopts a linear two-coordinate structure in both the solid state and in solution. The boron centre is stabilized by p π bonding from the mesityl groups and is free from coordination by the counterion or solvent molecules. This diarylborinium ion possesses exceptional Lewis acidity, accepting a pair of electrons from CO 2 to cause an unusual deoxygenation reaction. Borinium ions are two-coordinate boron cations that contain only four valence electrons on boron, and are difficult to isolate without electron donation from adjacent heteroatoms. Now, diarylborinium salts with no lone-pair donation from heteroatoms have been isolated, characterized and found to participate in an unusual reaction with CO 2 .</description><subject>639/638/406/910</subject><subject>639/638/406/911</subject><subject>639/638/549</subject><subject>Acidity</subject><subject>Analytical Chemistry</subject><subject>Biochemistry</subject><subject>Boron</subject><subject>Boron Compounds - chemistry</subject><subject>Carbon</subject><subject>Carbon dioxide</subject><subject>Carbon Dioxide - chemistry</subject><subject>Cations</subject><subject>Cations - chemistry</subject><subject>Chemical bonds</subject><subject>Chemical speciation</subject><subject>Chemistry</subject><subject>Chemistry/Food Science</subject><subject>Crystallography</subject><subject>Crystallography, X-Ray</subject><subject>Inorganic Chemistry</subject><subject>Ions</subject><subject>Lewis Acids - chemistry</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Models, Molecular</subject><subject>Molecular Structure</subject><subject>Organic Chemistry</subject><subject>Oxidation-Reduction</subject><subject>Physical Chemistry</subject><subject>Solvents</subject><subject>Spectroscopy</subject><issn>1755-4330</issn><issn>1755-4349</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><sourceid>ABUWG</sourceid><sourceid>AFKRA</sourceid><sourceid>AZQEC</sourceid><sourceid>BENPR</sourceid><sourceid>CCPQU</sourceid><sourceid>DWQXO</sourceid><sourceid>GNUQQ</sourceid><recordid>eNplkMtKAzEUhoMotlY3PoAMuBHL1GRyacZdHbxBwY2uQyaT1CmdpCYziDvfwTf0SUxtLaKb_4Tw8Z_DB8AxgiMEMb-w6lk3I5QTvgP6aExpSjDJd7dvDHvgIIQ5hIxixPZBLyOc8AzTPricJO2rS5VzvqqtbHVSOu9somRbx2G0bDtf21lSfL5_XA1jFJGwkZ0dgj0jF0EfbeYAPN1cPxZ36fTh9r6YTFNFGGpTprisCKFxNaFyXGVcjXNVZZogzpBBFdPUGMk1ix8xSkqMLnOFNFaGxRyAs3Xv0ruXTodWNHVQerGQVrsuCEQzjjHjBEb09A86d5238TqBGGWQUg5JpM7XlPIuBK-NWPq6kf5NIChWRsW3UbEyGuGTTWVXNrraoj8KIzBcA2G5EqX9r53_674A0SaAZA</recordid><startdate>20140601</startdate><enddate>20140601</enddate><creator>Shoji, Yoshiaki</creator><creator>Tanaka, Naoki</creator><creator>Mikami, Koichiro</creator><creator>Uchiyama, Masanobu</creator><creator>Fukushima, Takanori</creator><general>Nature Publishing Group UK</general><general>Nature Publishing Group</general><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>3V.</scope><scope>7QR</scope><scope>7X7</scope><scope>7XB</scope><scope>88E</scope><scope>8AO</scope><scope>8FD</scope><scope>8FE</scope><scope>8FG</scope><scope>8FH</scope><scope>8FI</scope><scope>8FJ</scope><scope>8FK</scope><scope>ABJCF</scope><scope>ABUWG</scope><scope>AFKRA</scope><scope>AZQEC</scope><scope>BBNVY</scope><scope>BENPR</scope><scope>BGLVJ</scope><scope>BHPHI</scope><scope>CCPQU</scope><scope>D1I</scope><scope>DWQXO</scope><scope>FR3</scope><scope>FYUFA</scope><scope>GHDGH</scope><scope>GNUQQ</scope><scope>HCIFZ</scope><scope>K9.</scope><scope>KB.</scope><scope>LK8</scope><scope>M0S</scope><scope>M1P</scope><scope>M7P</scope><scope>P64</scope><scope>PDBOC</scope><scope>PQEST</scope><scope>PQQKQ</scope><scope>PQUKI</scope><scope>7X8</scope></search><sort><creationdate>20140601</creationdate><title>A two-coordinate boron cation featuring C–B+–C bonding</title><author>Shoji, Yoshiaki ; Tanaka, Naoki ; Mikami, Koichiro ; Uchiyama, Masanobu ; Fukushima, Takanori</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c461t-6c8ad44553145a7d28c79cd2e41861f1d6e5ffa8e6418e64b54feb9c1e3cf61e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>639/638/406/910</topic><topic>639/638/406/911</topic><topic>639/638/549</topic><topic>Acidity</topic><topic>Analytical Chemistry</topic><topic>Biochemistry</topic><topic>Boron</topic><topic>Boron Compounds - chemistry</topic><topic>Carbon</topic><topic>Carbon dioxide</topic><topic>Carbon Dioxide - chemistry</topic><topic>Cations</topic><topic>Cations - chemistry</topic><topic>Chemical bonds</topic><topic>Chemical speciation</topic><topic>Chemistry</topic><topic>Chemistry/Food Science</topic><topic>Crystallography</topic><topic>Crystallography, X-Ray</topic><topic>Inorganic Chemistry</topic><topic>Ions</topic><topic>Lewis Acids - chemistry</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Models, Molecular</topic><topic>Molecular Structure</topic><topic>Organic Chemistry</topic><topic>Oxidation-Reduction</topic><topic>Physical Chemistry</topic><topic>Solvents</topic><topic>Spectroscopy</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Shoji, Yoshiaki</creatorcontrib><creatorcontrib>Tanaka, Naoki</creatorcontrib><creatorcontrib>Mikami, Koichiro</creatorcontrib><creatorcontrib>Uchiyama, Masanobu</creatorcontrib><creatorcontrib>Fukushima, Takanori</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>ProQuest Central (Corporate)</collection><collection>Chemoreception Abstracts</collection><collection>Health &amp; Medical Collection</collection><collection>ProQuest Central (purchase pre-March 2016)</collection><collection>Medical Database (Alumni Edition)</collection><collection>ProQuest Pharma Collection</collection><collection>Technology Research Database</collection><collection>ProQuest SciTech Collection</collection><collection>ProQuest Technology Collection</collection><collection>ProQuest Natural Science Collection</collection><collection>Hospital Premium Collection</collection><collection>Hospital Premium Collection (Alumni Edition)</collection><collection>ProQuest Central (Alumni) (purchase pre-March 2016)</collection><collection>Materials Science &amp; Engineering Collection</collection><collection>ProQuest Central (Alumni Edition)</collection><collection>ProQuest Central UK/Ireland</collection><collection>ProQuest Central Essentials</collection><collection>Biological Science Collection</collection><collection>ProQuest Central</collection><collection>Technology Collection</collection><collection>Natural Science Collection</collection><collection>ProQuest One Community College</collection><collection>ProQuest Materials Science Collection</collection><collection>ProQuest Central Korea</collection><collection>Engineering Research Database</collection><collection>Health Research Premium Collection</collection><collection>Health Research Premium Collection (Alumni)</collection><collection>ProQuest Central Student</collection><collection>SciTech Premium Collection</collection><collection>ProQuest Health &amp; Medical Complete (Alumni)</collection><collection>Materials Science Database</collection><collection>ProQuest Biological Science Collection</collection><collection>Health &amp; Medical Collection (Alumni Edition)</collection><collection>Medical Database</collection><collection>Biological Science Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>Materials Science Collection</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><collection>MEDLINE - Academic</collection><jtitle>Nature chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Shoji, Yoshiaki</au><au>Tanaka, Naoki</au><au>Mikami, Koichiro</au><au>Uchiyama, Masanobu</au><au>Fukushima, Takanori</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A two-coordinate boron cation featuring C–B+–C bonding</atitle><jtitle>Nature chemistry</jtitle><stitle>Nature Chem</stitle><addtitle>Nat Chem</addtitle><date>2014-06-01</date><risdate>2014</risdate><volume>6</volume><issue>6</issue><spage>498</spage><epage>503</epage><pages>498-503</pages><issn>1755-4330</issn><eissn>1755-4349</eissn><abstract>Two-coordinate boron cations (R 2 B + ), referred to as borinium ions, are chemical species in which the boron bears only four valence electrons, and that are isoelectronic with hypothetical carbon dications (R 2 C 2+ ). Although lone-pair-donating substituents such as amino groups have enabled the isolation of several borinium ions, diarylated and dialkylated borinium derivatives remain entirely unexplored. Here, we present the synthesis, structure and reactivity of the dimesitylborinium ion, which displays unexpectedly high thermal stability. X-ray crystallography and 11 B NMR spectroscopy, supported by density functional theory calculations, reveal that the borinium ion adopts a linear two-coordinate structure in both the solid state and in solution. The boron centre is stabilized by p π bonding from the mesityl groups and is free from coordination by the counterion or solvent molecules. This diarylborinium ion possesses exceptional Lewis acidity, accepting a pair of electrons from CO 2 to cause an unusual deoxygenation reaction. Borinium ions are two-coordinate boron cations that contain only four valence electrons on boron, and are difficult to isolate without electron donation from adjacent heteroatoms. Now, diarylborinium salts with no lone-pair donation from heteroatoms have been isolated, characterized and found to participate in an unusual reaction with CO 2 .</abstract><cop>London</cop><pub>Nature Publishing Group UK</pub><pmid>24848235</pmid><doi>10.1038/nchem.1948</doi><tpages>6</tpages></addata></record>
fulltext fulltext
identifier ISSN: 1755-4330
ispartof Nature chemistry, 2014-06, Vol.6 (6), p.498-503
issn 1755-4330
1755-4349
language eng
recordid cdi_proquest_miscellaneous_1528336840
source MEDLINE; Nature; Alma/SFX Local Collection
subjects 639/638/406/910
639/638/406/911
639/638/549
Acidity
Analytical Chemistry
Biochemistry
Boron
Boron Compounds - chemistry
Carbon
Carbon dioxide
Carbon Dioxide - chemistry
Cations
Cations - chemistry
Chemical bonds
Chemical speciation
Chemistry
Chemistry/Food Science
Crystallography
Crystallography, X-Ray
Inorganic Chemistry
Ions
Lewis Acids - chemistry
Magnetic Resonance Spectroscopy
Models, Molecular
Molecular Structure
Organic Chemistry
Oxidation-Reduction
Physical Chemistry
Solvents
Spectroscopy
title A two-coordinate boron cation featuring C–B+–C bonding
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-15T04%3A23%3A39IST&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%20two-coordinate%20boron%20cation%20featuring%20C%E2%80%93B+%E2%80%93C%20bonding&rft.jtitle=Nature%20chemistry&rft.au=Shoji,%20Yoshiaki&rft.date=2014-06-01&rft.volume=6&rft.issue=6&rft.spage=498&rft.epage=503&rft.pages=498-503&rft.issn=1755-4330&rft.eissn=1755-4349&rft_id=info:doi/10.1038/nchem.1948&rft_dat=%3Cproquest_cross%3E1528336840%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=1656055804&rft_id=info:pmid/24848235&rfr_iscdi=true