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...
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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 |
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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 & 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 & 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 & Medical Complete (Alumni)</collection><collection>Materials Science Database</collection><collection>ProQuest Biological Science Collection</collection><collection>Health & 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> |
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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 |
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