Characterization of hydrogen-substituted silylium ions in the condensed phase
Hydrogen-substituted silylium ions are long-sought reactive species. We report a protolysis strategy that chemoselectively cleaves either an Si-C(sp ) or an Si-H bond using a carborane acid to access the full series of [CHB H Br ] -stabilized R SiH , RSiH , and SiH cations, where bulky -butyl groups...
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| Veröffentlicht in: | Science (American Association for the Advancement of Science) 2019-07, Vol.365 (6449), p.168-172 |
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| container_title | Science (American Association for the Advancement of Science) |
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| creator | Wu, Qian Irran, Elisabeth Müller, Robert Kaupp, Martin Klare, Hendrik F T Oestreich, Martin |
| description | Hydrogen-substituted silylium ions are long-sought reactive species. We report a protolysis strategy that chemoselectively cleaves either an Si-C(sp
) or an Si-H bond using a carborane acid to access the full series of [CHB
H
Br
]
-stabilized R
SiH
, RSiH
, and SiH
cations, where bulky
-butyl groups at the silicon atom (R =
Bu) were crucial to avoid substituent redistribution. The crystallographically characterized molecular structures of [CHB
H
Br
]
-stabilized
Bu
HSi
and
BuH
Si
feature pyramidalization at the silicon atom, in accordance with that of
Bu
Si
[CHB
H
Br
]
Conversely, the silicon atom in the H
Si
cation adopts a trigonal-planar structure and is stabilized by two counteranions. This solid-state structure resembles that of the corresponding Brønsted acid. |
| doi_str_mv | 10.1126/science.aax9184 |
| format | Article |
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) or an Si-H bond using a carborane acid to access the full series of [CHB
H
Br
]
-stabilized R
SiH
, RSiH
, and SiH
cations, where bulky
-butyl groups at the silicon atom (R =
Bu) were crucial to avoid substituent redistribution. The crystallographically characterized molecular structures of [CHB
H
Br
]
-stabilized
Bu
HSi
and
BuH
Si
feature pyramidalization at the silicon atom, in accordance with that of
Bu
Si
[CHB
H
Br
]
Conversely, the silicon atom in the H
Si
cation adopts a trigonal-planar structure and is stabilized by two counteranions. This solid-state structure resembles that of the corresponding Brønsted acid.</description><identifier>ISSN: 0036-8075</identifier><identifier>EISSN: 1095-9203</identifier><identifier>DOI: 10.1126/science.aax9184</identifier><identifier>PMID: 31296768</identifier><language>eng</language><publisher>United States: The American Association for the Advancement of Science</publisher><subject>Acids ; Benzene ; Bonding strength ; Bromine ; Carborane ; Cations ; Crystallography ; Hydrogen bonds ; Planar structures ; Silicon ; Substitutes</subject><ispartof>Science (American Association for the Advancement of Science), 2019-07, Vol.365 (6449), p.168-172</ispartof><rights>Copyright © 2019 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.</rights><rights>Copyright © 2019 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c362t-bd41f463b0f88198c32788e56825307be1de8563fe2a64066d2f03bc0cff945a3</citedby><cites>FETCH-LOGICAL-c362t-bd41f463b0f88198c32788e56825307be1de8563fe2a64066d2f03bc0cff945a3</cites><orcidid>0000-0003-0983-3095 ; 0000-0003-3748-6609 ; 0000-0003-1582-2819 ; 0000-0002-1487-9218 ; 0000-0002-9135-8125 ; 0000-0001-6098-1996</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,2884,2885,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/31296768$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Wu, Qian</creatorcontrib><creatorcontrib>Irran, Elisabeth</creatorcontrib><creatorcontrib>Müller, Robert</creatorcontrib><creatorcontrib>Kaupp, Martin</creatorcontrib><creatorcontrib>Klare, Hendrik F T</creatorcontrib><creatorcontrib>Oestreich, Martin</creatorcontrib><title>Characterization of hydrogen-substituted silylium ions in the condensed phase</title><title>Science (American Association for the Advancement of Science)</title><addtitle>Science</addtitle><description>Hydrogen-substituted silylium ions are long-sought reactive species. We report a protolysis strategy that chemoselectively cleaves either an Si-C(sp
) or an Si-H bond using a carborane acid to access the full series of [CHB
H
Br
]
-stabilized R
SiH
, RSiH
, and SiH
cations, where bulky
-butyl groups at the silicon atom (R =
Bu) were crucial to avoid substituent redistribution. The crystallographically characterized molecular structures of [CHB
H
Br
]
-stabilized
Bu
HSi
and
BuH
Si
feature pyramidalization at the silicon atom, in accordance with that of
Bu
Si
[CHB
H
Br
]
Conversely, the silicon atom in the H
Si
cation adopts a trigonal-planar structure and is stabilized by two counteranions. This solid-state structure resembles that of the corresponding Brønsted acid.</description><subject>Acids</subject><subject>Benzene</subject><subject>Bonding strength</subject><subject>Bromine</subject><subject>Carborane</subject><subject>Cations</subject><subject>Crystallography</subject><subject>Hydrogen bonds</subject><subject>Planar structures</subject><subject>Silicon</subject><subject>Substitutes</subject><issn>0036-8075</issn><issn>1095-9203</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNpdkDtPwzAUhS0EoqUws6FILCxp_UgcZ0QVLwnEAnPkONfEVWIX25Eov55AAwPTHc53jq4-hM4JXhJC-SooA1bBUsqPkojsAM0JLvO0pJgdojnGjKcCF_kMnYSwwXjMSnaMZozQkhdczNHTupVeqgjefMponE2cTtpd490b2DQMdYgmDhGaJJhu15mhT0YoJMYmsYVEOduADWO8bWWAU3SkZRfgbLoL9Hp787K-Tx-f7x7W14-pYpzGtG4yojPOaqyFIKVQjBZCQM4FzRkuaiANiJwzDVTyDHPeUI1ZrbDSusxyyRboar-79e59gBCr3gQFXSctuCFUlOZFgRkTfEQv_6EbN3g7fvdDUSoyRkdqtaeUdyF40NXWm176XUVw9W26mkxXk-mxcTHtDnUPzR__q5Z9AXZUe_g</recordid><startdate>20190712</startdate><enddate>20190712</enddate><creator>Wu, Qian</creator><creator>Irran, Elisabeth</creator><creator>Müller, Robert</creator><creator>Kaupp, Martin</creator><creator>Klare, Hendrik F T</creator><creator>Oestreich, Martin</creator><general>The American Association for the Advancement of Science</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QF</scope><scope>7QG</scope><scope>7QL</scope><scope>7QP</scope><scope>7QQ</scope><scope>7QR</scope><scope>7SC</scope><scope>7SE</scope><scope>7SN</scope><scope>7SP</scope><scope>7SR</scope><scope>7SS</scope><scope>7T7</scope><scope>7TA</scope><scope>7TB</scope><scope>7TK</scope><scope>7TM</scope><scope>7U5</scope><scope>7U9</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>F28</scope><scope>FR3</scope><scope>H8D</scope><scope>H8G</scope><scope>H94</scope><scope>JG9</scope><scope>JQ2</scope><scope>K9.</scope><scope>KR7</scope><scope>L7M</scope><scope>L~C</scope><scope>L~D</scope><scope>M7N</scope><scope>P64</scope><scope>RC3</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0003-0983-3095</orcidid><orcidid>https://orcid.org/0000-0003-3748-6609</orcidid><orcidid>https://orcid.org/0000-0003-1582-2819</orcidid><orcidid>https://orcid.org/0000-0002-1487-9218</orcidid><orcidid>https://orcid.org/0000-0002-9135-8125</orcidid><orcidid>https://orcid.org/0000-0001-6098-1996</orcidid></search><sort><creationdate>20190712</creationdate><title>Characterization of hydrogen-substituted silylium ions in the condensed phase</title><author>Wu, Qian ; Irran, Elisabeth ; Müller, Robert ; Kaupp, Martin ; Klare, Hendrik F T ; Oestreich, Martin</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c362t-bd41f463b0f88198c32788e56825307be1de8563fe2a64066d2f03bc0cff945a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Acids</topic><topic>Benzene</topic><topic>Bonding strength</topic><topic>Bromine</topic><topic>Carborane</topic><topic>Cations</topic><topic>Crystallography</topic><topic>Hydrogen bonds</topic><topic>Planar structures</topic><topic>Silicon</topic><topic>Substitutes</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Wu, Qian</creatorcontrib><creatorcontrib>Irran, Elisabeth</creatorcontrib><creatorcontrib>Müller, Robert</creatorcontrib><creatorcontrib>Kaupp, Martin</creatorcontrib><creatorcontrib>Klare, Hendrik F T</creatorcontrib><creatorcontrib>Oestreich, Martin</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Aluminium Industry Abstracts</collection><collection>Animal Behavior Abstracts</collection><collection>Bacteriology Abstracts (Microbiology B)</collection><collection>Calcium & Calcified Tissue Abstracts</collection><collection>Ceramic Abstracts</collection><collection>Chemoreception Abstracts</collection><collection>Computer and Information Systems Abstracts</collection><collection>Corrosion Abstracts</collection><collection>Ecology Abstracts</collection><collection>Electronics & Communications Abstracts</collection><collection>Engineered Materials Abstracts</collection><collection>Entomology Abstracts (Full archive)</collection><collection>Industrial and Applied Microbiology Abstracts (Microbiology A)</collection><collection>Materials Business File</collection><collection>Mechanical & Transportation Engineering Abstracts</collection><collection>Neurosciences Abstracts</collection><collection>Nucleic Acids Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Virology and AIDS Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>ANTE: Abstracts in New Technology & Engineering</collection><collection>Engineering Research Database</collection><collection>Aerospace Database</collection><collection>Copper Technical Reference Library</collection><collection>AIDS and Cancer Research Abstracts</collection><collection>Materials Research Database</collection><collection>ProQuest Computer Science Collection</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>Civil Engineering Abstracts</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>Computer and Information Systems Abstracts Academic</collection><collection>Computer and Information Systems Abstracts Professional</collection><collection>Algology Mycology and Protozoology Abstracts (Microbiology C)</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>Genetics Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Science (American Association for the Advancement of Science)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Wu, Qian</au><au>Irran, Elisabeth</au><au>Müller, Robert</au><au>Kaupp, Martin</au><au>Klare, Hendrik F T</au><au>Oestreich, Martin</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Characterization of hydrogen-substituted silylium ions in the condensed phase</atitle><jtitle>Science (American Association for the Advancement of Science)</jtitle><addtitle>Science</addtitle><date>2019-07-12</date><risdate>2019</risdate><volume>365</volume><issue>6449</issue><spage>168</spage><epage>172</epage><pages>168-172</pages><issn>0036-8075</issn><eissn>1095-9203</eissn><abstract>Hydrogen-substituted silylium ions are long-sought reactive species. We report a protolysis strategy that chemoselectively cleaves either an Si-C(sp
) or an Si-H bond using a carborane acid to access the full series of [CHB
H
Br
]
-stabilized R
SiH
, RSiH
, and SiH
cations, where bulky
-butyl groups at the silicon atom (R =
Bu) were crucial to avoid substituent redistribution. The crystallographically characterized molecular structures of [CHB
H
Br
]
-stabilized
Bu
HSi
and
BuH
Si
feature pyramidalization at the silicon atom, in accordance with that of
Bu
Si
[CHB
H
Br
]
Conversely, the silicon atom in the H
Si
cation adopts a trigonal-planar structure and is stabilized by two counteranions. This solid-state structure resembles that of the corresponding Brønsted acid.</abstract><cop>United States</cop><pub>The American Association for the Advancement of Science</pub><pmid>31296768</pmid><doi>10.1126/science.aax9184</doi><tpages>5</tpages><orcidid>https://orcid.org/0000-0003-0983-3095</orcidid><orcidid>https://orcid.org/0000-0003-3748-6609</orcidid><orcidid>https://orcid.org/0000-0003-1582-2819</orcidid><orcidid>https://orcid.org/0000-0002-1487-9218</orcidid><orcidid>https://orcid.org/0000-0002-9135-8125</orcidid><orcidid>https://orcid.org/0000-0001-6098-1996</orcidid></addata></record> |
| fulltext | fulltext |
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| ispartof | Science (American Association for the Advancement of Science), 2019-07, Vol.365 (6449), p.168-172 |
| issn | 0036-8075 1095-9203 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_2257703386 |
| source | American Association for the Advancement of Science |
| subjects | Acids Benzene Bonding strength Bromine Carborane Cations Crystallography Hydrogen bonds Planar structures Silicon Substitutes |
| title | Characterization of hydrogen-substituted silylium ions in the condensed phase |
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