A Free Silanide from Nucleophilic Substitution at Silicon(II)
A computationally guided synthetic route to a free silanide derived from tris(3‐methylindol‐2‐yl)methane ([(tmim)Si]−) through nucleophilic substitution on the SiII precursor (Idipp)SiCl2 is reported (Idipp=2,3‐dihydro‐1,3‐bis(2,6‐diisopropylphenyl)‐1H‐imidazol‐2‐ylidene). This approach circumvents...
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| Veröffentlicht in: | Chemistry : a European journal 2018-08, Vol.24 (47), p.12236-12240 |
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| creator | Witteman, Léon Evers, Tim Lutz, Martin Moret, Marc‐Etienne |
| description | A computationally guided synthetic route to a free silanide derived from tris(3‐methylindol‐2‐yl)methane ([(tmim)Si]−) through nucleophilic substitution on the SiII precursor (Idipp)SiCl2 is reported (Idipp=2,3‐dihydro‐1,3‐bis(2,6‐diisopropylphenyl)‐1H‐imidazol‐2‐ylidene). This approach circumvents the need for strained tetrahedral silanes as synthetic intermediates. Computational investigations show that the electron‐donating properties of [(tmim)Si]− are close to those of PMe3. Experimentally, the [(tmim)Si]− anion is shown to undergo clean complexation to the base metal salts CuCl and FeCl2, demonstrating the potential utility as a supporting ligand.
Relaxed bicycle: A bicyclic silanide was synthesized by nucleophilic substitution of an indolide‐based trianionic fragment on a neutral SiII precursor, avoiding strained tetrahedral SiIV intermediates. The silanide forms coordination complexes with first‐row transition‐metal salts, such as CuCl and FeCl2, suggesting the utility as a supporting ligand. |
| doi_str_mv | 10.1002/chem.201801435 |
| format | Article |
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Relaxed bicycle: A bicyclic silanide was synthesized by nucleophilic substitution of an indolide‐based trianionic fragment on a neutral SiII precursor, avoiding strained tetrahedral SiIV intermediates. The silanide forms coordination complexes with first‐row transition‐metal salts, such as CuCl and FeCl2, suggesting the utility as a supporting ligand.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.201801435</identifier><identifier>PMID: 29577491</identifier><language>eng</language><publisher>Germany: Wiley Subscription Services, Inc</publisher><subject>Base metal ; Chemistry ; Communication ; Communications ; Computer applications ; constrained geometry ; Copper chloride ; density functional theory ; Intermediates ; Iron chlorides ; metal complexes ; Salts ; Silanes ; Silicon ; silyl ligand ; Substitutes</subject><ispartof>Chemistry : a European journal, 2018-08, Vol.24 (47), p.12236-12240</ispartof><rights>2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.</rights><rights>2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5055-f7b800c58513c158c4d8ba0e5cc7f1cad3ae9bdfe7a2e285dc713c129ff2aa13</citedby><cites>FETCH-LOGICAL-c5055-f7b800c58513c158c4d8ba0e5cc7f1cad3ae9bdfe7a2e285dc713c129ff2aa13</cites><orcidid>0000-0003-2189-830X ; 0000-0002-3137-6073</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%2Fchem.201801435$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.201801435$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>230,314,776,780,881,1411,27901,27902,45550,45551</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29577491$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Witteman, Léon</creatorcontrib><creatorcontrib>Evers, Tim</creatorcontrib><creatorcontrib>Lutz, Martin</creatorcontrib><creatorcontrib>Moret, Marc‐Etienne</creatorcontrib><title>A Free Silanide from Nucleophilic Substitution at Silicon(II)</title><title>Chemistry : a European journal</title><addtitle>Chemistry</addtitle><description>A computationally guided synthetic route to a free silanide derived from tris(3‐methylindol‐2‐yl)methane ([(tmim)Si]−) through nucleophilic substitution on the SiII precursor (Idipp)SiCl2 is reported (Idipp=2,3‐dihydro‐1,3‐bis(2,6‐diisopropylphenyl)‐1H‐imidazol‐2‐ylidene). This approach circumvents the need for strained tetrahedral silanes as synthetic intermediates. Computational investigations show that the electron‐donating properties of [(tmim)Si]− are close to those of PMe3. Experimentally, the [(tmim)Si]− anion is shown to undergo clean complexation to the base metal salts CuCl and FeCl2, demonstrating the potential utility as a supporting ligand.
Relaxed bicycle: A bicyclic silanide was synthesized by nucleophilic substitution of an indolide‐based trianionic fragment on a neutral SiII precursor, avoiding strained tetrahedral SiIV intermediates. The silanide forms coordination complexes with first‐row transition‐metal salts, such as CuCl and FeCl2, suggesting the utility as a supporting ligand.</description><subject>Base metal</subject><subject>Chemistry</subject><subject>Communication</subject><subject>Communications</subject><subject>Computer applications</subject><subject>constrained geometry</subject><subject>Copper chloride</subject><subject>density functional theory</subject><subject>Intermediates</subject><subject>Iron chlorides</subject><subject>metal complexes</subject><subject>Salts</subject><subject>Silanes</subject><subject>Silicon</subject><subject>silyl ligand</subject><subject>Substitutes</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><recordid>eNqFkTtPwzAURi0EglJYGVEkFhhSbCe24wEkVFGoxGOA3XKcG2qUxMVOQPx7EhXKY2G6g4-P7nc_hA4InhCM6alZQD2hmGSYpAnbQCPCKIkTwdkmGmGZipizRO6g3RCeMcaSJ8k22qGSCZFKMkJnF9HMA0QPttKNLSAqvauju85U4JYLW1kTPXR5aG3btdY1kW4H1BrXHM_nJ3toq9RVgP3POUaPs8vH6XV8c381n17cxIZhxuJS5BnGhmWMJIawzKRFlmsMzBhREqOLRIPMixKEpkAzVhgxgFSWJdWaJGN0vtIuu7yGwkDTel2ppbe19u_Kaat-vzR2oZ7cq-KE4pQPguNPgXcvHYRW1TYYqPrM4LqghgNynvGU9-jRH_TZdb7p0_WUJIxRwbOemqwo410IHsr1MgSroRg1FKPWxfQfDn9GWONfTfSAXAFvtoL3f3Rqen15-y3_AGTcmko</recordid><startdate>20180822</startdate><enddate>20180822</enddate><creator>Witteman, Léon</creator><creator>Evers, Tim</creator><creator>Lutz, Martin</creator><creator>Moret, Marc‐Etienne</creator><general>Wiley Subscription Services, Inc</general><general>John Wiley and Sons Inc</general><scope>24P</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>K9.</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0003-2189-830X</orcidid><orcidid>https://orcid.org/0000-0002-3137-6073</orcidid></search><sort><creationdate>20180822</creationdate><title>A Free Silanide from Nucleophilic Substitution at Silicon(II)</title><author>Witteman, Léon ; Evers, Tim ; Lutz, Martin ; Moret, Marc‐Etienne</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5055-f7b800c58513c158c4d8ba0e5cc7f1cad3ae9bdfe7a2e285dc713c129ff2aa13</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Base metal</topic><topic>Chemistry</topic><topic>Communication</topic><topic>Communications</topic><topic>Computer applications</topic><topic>constrained geometry</topic><topic>Copper chloride</topic><topic>density functional theory</topic><topic>Intermediates</topic><topic>Iron chlorides</topic><topic>metal complexes</topic><topic>Salts</topic><topic>Silanes</topic><topic>Silicon</topic><topic>silyl ligand</topic><topic>Substitutes</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Witteman, Léon</creatorcontrib><creatorcontrib>Evers, Tim</creatorcontrib><creatorcontrib>Lutz, Martin</creatorcontrib><creatorcontrib>Moret, Marc‐Etienne</creatorcontrib><collection>Wiley Online Library Open Access</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Witteman, Léon</au><au>Evers, Tim</au><au>Lutz, Martin</au><au>Moret, Marc‐Etienne</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Free Silanide from Nucleophilic Substitution at Silicon(II)</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry</addtitle><date>2018-08-22</date><risdate>2018</risdate><volume>24</volume><issue>47</issue><spage>12236</spage><epage>12240</epage><pages>12236-12240</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>A computationally guided synthetic route to a free silanide derived from tris(3‐methylindol‐2‐yl)methane ([(tmim)Si]−) through nucleophilic substitution on the SiII precursor (Idipp)SiCl2 is reported (Idipp=2,3‐dihydro‐1,3‐bis(2,6‐diisopropylphenyl)‐1H‐imidazol‐2‐ylidene). This approach circumvents the need for strained tetrahedral silanes as synthetic intermediates. Computational investigations show that the electron‐donating properties of [(tmim)Si]− are close to those of PMe3. Experimentally, the [(tmim)Si]− anion is shown to undergo clean complexation to the base metal salts CuCl and FeCl2, demonstrating the potential utility as a supporting ligand.
Relaxed bicycle: A bicyclic silanide was synthesized by nucleophilic substitution of an indolide‐based trianionic fragment on a neutral SiII precursor, avoiding strained tetrahedral SiIV intermediates. The silanide forms coordination complexes with first‐row transition‐metal salts, such as CuCl and FeCl2, suggesting the utility as a supporting ligand.</abstract><cop>Germany</cop><pub>Wiley Subscription Services, Inc</pub><pmid>29577491</pmid><doi>10.1002/chem.201801435</doi><tpages>5</tpages><orcidid>https://orcid.org/0000-0003-2189-830X</orcidid><orcidid>https://orcid.org/0000-0002-3137-6073</orcidid><oa>free_for_read</oa></addata></record> |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Base metal Chemistry Communication Communications Computer applications constrained geometry Copper chloride density functional theory Intermediates Iron chlorides metal complexes Salts Silanes Silicon silyl ligand Substitutes |
| title | A Free Silanide from Nucleophilic Substitution at Silicon(II) |
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