Carborane acids. New "strong yet gentle" acids for organic and inorganic chemistry
Icosahedral carborane anions such as CHB11Cl11- are amongst the least coordinating, most chemically inert anions known. They are also amongst the least basic, so their conjugate acids, H(carborane), are superacids (i.e. stronger than 100% H2SO4). Acidity scale measurements indicate that H(CHB11Cl11)...
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| Veröffentlicht in: | Chemical communications (Cambridge, England) England), 2005-04 (13), p.1669-1677 |
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| creator | Reed, Christopher A |
| description | Icosahedral carborane anions such as CHB11Cl11- are amongst the least coordinating, most chemically inert anions known. They are also amongst the least basic, so their conjugate acids, H(carborane), are superacids (i.e. stronger than 100% H2SO4). Acidity scale measurements indicate that H(CHB11Cl11) is the strongest pure Brønsted acid presently known, surpassing triflic and fluorosulfuric acid. Nevertheless, it is also an extremely gentle acid--because its conjugate base engages in so little chemistry. Carborane acids separate protic acidity from anion nucleophilicity and destructive oxidative capacity in the conjugate base, to a degree not previously achieved. As a result, many long-sought, highly acidic, reactive cations such as protonated benzene (C6H7+), protonated C60(HC60+), tertiary carbocations (R3C+), vinyl cations (R2C=C(+)-R), silylium ions (R3Si+) and discrete hydronium ions (H3O+, H5O2+ etc.) can be readily isolated as carborane salts and characterized at room temperature by X-ray crystallography. |
| doi_str_mv | 10.1039/b415425h |
| format | Article |
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Carborane acids separate protic acidity from anion nucleophilicity and destructive oxidative capacity in the conjugate base, to a degree not previously achieved. As a result, many long-sought, highly acidic, reactive cations such as protonated benzene (C6H7+), protonated C60(HC60+), tertiary carbocations (R3C+), vinyl cations (R2C=C(+)-R), silylium ions (R3Si+) and discrete hydronium ions (H3O+, H5O2+ etc.) can be readily isolated as carborane salts and characterized at room temperature by X-ray crystallography.</description><identifier>ISSN: 1359-7345</identifier><identifier>EISSN: 1364-548X</identifier><identifier>DOI: 10.1039/b415425h</identifier><identifier>PMID: 15791295</identifier><language>eng</language><publisher>England</publisher><subject>Acids - chemistry ; Alkanes - chemistry ; Alkylation ; Anions - chemistry ; Carbonates - chemistry ; Chemistry, Inorganic - methods ; Chemistry, Organic - methods ; Crystallography, X-Ray ; Hydrogen-Ion Concentration ; Ions - chemistry ; Models, Molecular ; Molecular Structure ; Onium Compounds - chemistry ; Oxides - chemistry ; Protons</subject><ispartof>Chemical communications (Cambridge, England), 2005-04 (13), p.1669-1677</ispartof><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c401t-8c9d78ef5c99b2010230654f5d46685de1f3514ad6010211165fd478d3e2a3683</citedby><cites>FETCH-LOGICAL-c401t-8c9d78ef5c99b2010230654f5d46685de1f3514ad6010211165fd478d3e2a3683</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,781,785,2832,27929,27930</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15791295$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Reed, Christopher A</creatorcontrib><title>Carborane acids. New "strong yet gentle" acids for organic and inorganic chemistry</title><title>Chemical communications (Cambridge, England)</title><addtitle>Chem Commun (Camb)</addtitle><description>Icosahedral carborane anions such as CHB11Cl11- are amongst the least coordinating, most chemically inert anions known. They are also amongst the least basic, so their conjugate acids, H(carborane), are superacids (i.e. stronger than 100% H2SO4). Acidity scale measurements indicate that H(CHB11Cl11) is the strongest pure Brønsted acid presently known, surpassing triflic and fluorosulfuric acid. Nevertheless, it is also an extremely gentle acid--because its conjugate base engages in so little chemistry. Carborane acids separate protic acidity from anion nucleophilicity and destructive oxidative capacity in the conjugate base, to a degree not previously achieved. As a result, many long-sought, highly acidic, reactive cations such as protonated benzene (C6H7+), protonated C60(HC60+), tertiary carbocations (R3C+), vinyl cations (R2C=C(+)-R), silylium ions (R3Si+) and discrete hydronium ions (H3O+, H5O2+ etc.) can be readily isolated as carborane salts and characterized at room temperature by X-ray crystallography.</description><subject>Acids - chemistry</subject><subject>Alkanes - chemistry</subject><subject>Alkylation</subject><subject>Anions - chemistry</subject><subject>Carbonates - chemistry</subject><subject>Chemistry, Inorganic - methods</subject><subject>Chemistry, Organic - methods</subject><subject>Crystallography, X-Ray</subject><subject>Hydrogen-Ion Concentration</subject><subject>Ions - chemistry</subject><subject>Models, Molecular</subject><subject>Molecular Structure</subject><subject>Onium Compounds - chemistry</subject><subject>Oxides - chemistry</subject><subject>Protons</subject><issn>1359-7345</issn><issn>1364-548X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpFkE1Lw0AQhhdRbK2Cv0CWHsRL6k52Z5McbVErFAVR8BY2-9FG0qTupkj_vampOJeZYZ55h3kJuQQ2Acaz20IAihhXR2QIXIoIRfpxvK8xixIucEDOQvhkXQCmp2QAmGQQZzgkrzPli8ar2lKlSxMm9Nl-03FofVMv6c62dGnrtrLjfkxd42njl6ouNVW1oWX91-mVXZfd3u6cnDhVBXtxyCPy_nD_NptHi5fHp9ndItKCQRulOjNJah3qLCtiBizmTKJwaISUKRoLjiMIZeR-BgASnRFJariNFZcpH5HrXnfjm6-tDW3e3de2qrpnmm3IZYLIkl_wpge1b0Lw1uUbX66V3-XA8r1_-bT3b96hVwfNbbG25h88GMZ_AOPxaMk</recordid><startdate>20050407</startdate><enddate>20050407</enddate><creator>Reed, Christopher A</creator><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>7X8</scope></search><sort><creationdate>20050407</creationdate><title>Carborane acids. 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New "strong yet gentle" acids for organic and inorganic chemistry</atitle><jtitle>Chemical communications (Cambridge, England)</jtitle><addtitle>Chem Commun (Camb)</addtitle><date>2005-04-07</date><risdate>2005</risdate><issue>13</issue><spage>1669</spage><epage>1677</epage><pages>1669-1677</pages><issn>1359-7345</issn><eissn>1364-548X</eissn><abstract>Icosahedral carborane anions such as CHB11Cl11- are amongst the least coordinating, most chemically inert anions known. They are also amongst the least basic, so their conjugate acids, H(carborane), are superacids (i.e. stronger than 100% H2SO4). Acidity scale measurements indicate that H(CHB11Cl11) is the strongest pure Brønsted acid presently known, surpassing triflic and fluorosulfuric acid. Nevertheless, it is also an extremely gentle acid--because its conjugate base engages in so little chemistry. Carborane acids separate protic acidity from anion nucleophilicity and destructive oxidative capacity in the conjugate base, to a degree not previously achieved. As a result, many long-sought, highly acidic, reactive cations such as protonated benzene (C6H7+), protonated C60(HC60+), tertiary carbocations (R3C+), vinyl cations (R2C=C(+)-R), silylium ions (R3Si+) and discrete hydronium ions (H3O+, H5O2+ etc.) can be readily isolated as carborane salts and characterized at room temperature by X-ray crystallography.</abstract><cop>England</cop><pmid>15791295</pmid><doi>10.1039/b415425h</doi><tpages>9</tpages><oa>free_for_read</oa></addata></record> |
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| ispartof | Chemical communications (Cambridge, England), 2005-04 (13), p.1669-1677 |
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| source | MEDLINE; Royal Society Of Chemistry Journals; Royal Society of Chemistry Journals Archive (1841-2007); Alma/SFX Local Collection |
| subjects | Acids - chemistry Alkanes - chemistry Alkylation Anions - chemistry Carbonates - chemistry Chemistry, Inorganic - methods Chemistry, Organic - methods Crystallography, X-Ray Hydrogen-Ion Concentration Ions - chemistry Models, Molecular Molecular Structure Onium Compounds - chemistry Oxides - chemistry Protons |
| title | Carborane acids. New "strong yet gentle" acids for organic and inorganic chemistry |
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