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Confined Lewis Pairs: Investigation of the X - →Si 20 Interaction in Halogen-Encapsulating Silafulleranes
A joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Si Y ] (X=F-I; Y=F-I, H, Me, Et) and -[Cl@Si H Y ] (Y=F-I) is presented. First, we evaluated the structure-determining template effect of Cl in a systematic series of concave silapolyquinane model systems. Secon...
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| Published in: | Angewandte Chemie International Edition 2024-02, Vol.63 (6), p.e202314238 |
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| Main Authors: | , , , , , , , , , |
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| Language: | English |
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| cites | cdi_FETCH-LOGICAL-c1073-714bbbc912c25e49b3a81ec04381846def207d5f26639a894685daecb4363efc3 |
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| container_issue | 6 |
| container_start_page | e202314238 |
| container_title | Angewandte Chemie International Edition |
| container_volume | 63 |
| creator | Gasevic, Thomas Bamberg, Marcel Wicke, Julius Bolte, Michael Virovets, Alexander Lerner, Hans-Wolfram Grimme, Stefan Hansen, Andreas Wagner, Matthias Bursch, Markus |
| description | A joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Si
Y
]
(X=F-I; Y=F-I, H, Me, Et) and
-[Cl@Si
H
Y
]
(Y=F-I) is presented. First, we evaluated the structure-determining template effect of Cl
in a systematic series of concave silapolyquinane model systems. Second, we investigated the X
→Si
interaction energy (
) as a function of X
and Y and found the largest
values for electron-withdrawing exohedral substituents Y. Given that X
ions can be considered as Lewis bases and empty Si
Y
clusters as Lewis acids, we classify our inseparable host-guest complexes [X@Si
Y
]
as "confined Lewis pairs". Third,
Cl NMR spectroscopy proved to be highly diagnostic for an experimental assessment of the Cl
→Si
interaction as the paramagnetic shielding and, in turn,
(
Cl) of the endohedral Cl
ion correlate inversely with
. Finally, we disclose the synthesis of [PPN][Cl@Si
Y
] (Y=Me, Et, Br) and provide a thorough characterization of these new silafulleranes. |
| doi_str_mv | 10.1002/anie.202314238 |
| format | article |
| fullrecord | <record><control><sourceid>pubmed_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1002_anie_202314238</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>38059423</sourcerecordid><originalsourceid>FETCH-LOGICAL-c1073-714bbbc912c25e49b3a81ec04381846def207d5f26639a894685daecb4363efc3</originalsourceid><addsrcrecordid>eNo9kNFKwzAUQIMobk5ffZT8QGeSm7apbzKmGwwUpuBbSdObGe3S0WyKP-AH-Il-iZnTPeVCzrlcDiHnnA05Y-JSe4dDwQRwKUAdkD5PBU8gz-EwzhIgyVXKe-QkhJfIK8WyY9IDxdIiCn3yOmq9dR5rOsN3F-i9dl24olP_hmHtFnrtWk9bS9fPSJ9oQr8_v-aOChaJNXba_P47Tye6aRfok7E3ehU2TRT9gs5do-2maSLpMZySI6ubgGd_74A83owfRpNkdnc7HV3PEsNZHg_msqoqU3BhRIqyqEArjoZJUFzJrEYrWF6nVmQZFFoVMlNprdFUEjJAa2BAhru9pmtD6NCWq84tdfdRclZuq5XbauW-WhQudsJqUy2x3uP_meAH_RNpSA</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Confined Lewis Pairs: Investigation of the X - →Si 20 Interaction in Halogen-Encapsulating Silafulleranes</title><source>Wiley</source><creator>Gasevic, Thomas ; Bamberg, Marcel ; Wicke, Julius ; Bolte, Michael ; Virovets, Alexander ; Lerner, Hans-Wolfram ; Grimme, Stefan ; Hansen, Andreas ; Wagner, Matthias ; Bursch, Markus</creator><creatorcontrib>Gasevic, Thomas ; Bamberg, Marcel ; Wicke, Julius ; Bolte, Michael ; Virovets, Alexander ; Lerner, Hans-Wolfram ; Grimme, Stefan ; Hansen, Andreas ; Wagner, Matthias ; Bursch, Markus</creatorcontrib><description>A joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Si
Y
]
(X=F-I; Y=F-I, H, Me, Et) and
-[Cl@Si
H
Y
]
(Y=F-I) is presented. First, we evaluated the structure-determining template effect of Cl
in a systematic series of concave silapolyquinane model systems. Second, we investigated the X
→Si
interaction energy (
) as a function of X
and Y and found the largest
values for electron-withdrawing exohedral substituents Y. Given that X
ions can be considered as Lewis bases and empty Si
Y
clusters as Lewis acids, we classify our inseparable host-guest complexes [X@Si
Y
]
as "confined Lewis pairs". Third,
Cl NMR spectroscopy proved to be highly diagnostic for an experimental assessment of the Cl
→Si
interaction as the paramagnetic shielding and, in turn,
(
Cl) of the endohedral Cl
ion correlate inversely with
. Finally, we disclose the synthesis of [PPN][Cl@Si
Y
] (Y=Me, Et, Br) and provide a thorough characterization of these new silafulleranes.</description><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.202314238</identifier><identifier>PMID: 38059423</identifier><language>eng</language><publisher>Germany</publisher><ispartof>Angewandte Chemie International Edition, 2024-02, Vol.63 (6), p.e202314238</ispartof><rights>2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1073-714bbbc912c25e49b3a81ec04381846def207d5f26639a894685daecb4363efc3</citedby><cites>FETCH-LOGICAL-c1073-714bbbc912c25e49b3a81ec04381846def207d5f26639a894685daecb4363efc3</cites><orcidid>0000-0003-4864-1758 ; 0000-0002-8843-8503 ; 0000-0003-1803-7947 ; 0000-0003-1659-8206 ; 0000-0001-6711-5804 ; 0009-0004-5735-136X ; 0000-0001-6044-5077 ; 0000-0001-5806-8276 ; 0000-0001-5296-6251 ; 0000-0002-5844-4371</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27923,27924</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/38059423$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Gasevic, Thomas</creatorcontrib><creatorcontrib>Bamberg, Marcel</creatorcontrib><creatorcontrib>Wicke, Julius</creatorcontrib><creatorcontrib>Bolte, Michael</creatorcontrib><creatorcontrib>Virovets, Alexander</creatorcontrib><creatorcontrib>Lerner, Hans-Wolfram</creatorcontrib><creatorcontrib>Grimme, Stefan</creatorcontrib><creatorcontrib>Hansen, Andreas</creatorcontrib><creatorcontrib>Wagner, Matthias</creatorcontrib><creatorcontrib>Bursch, Markus</creatorcontrib><title>Confined Lewis Pairs: Investigation of the X - →Si 20 Interaction in Halogen-Encapsulating Silafulleranes</title><title>Angewandte Chemie International Edition</title><addtitle>Angew Chem Int Ed Engl</addtitle><description>A joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Si
Y
]
(X=F-I; Y=F-I, H, Me, Et) and
-[Cl@Si
H
Y
]
(Y=F-I) is presented. First, we evaluated the structure-determining template effect of Cl
in a systematic series of concave silapolyquinane model systems. Second, we investigated the X
→Si
interaction energy (
) as a function of X
and Y and found the largest
values for electron-withdrawing exohedral substituents Y. Given that X
ions can be considered as Lewis bases and empty Si
Y
clusters as Lewis acids, we classify our inseparable host-guest complexes [X@Si
Y
]
as "confined Lewis pairs". Third,
Cl NMR spectroscopy proved to be highly diagnostic for an experimental assessment of the Cl
→Si
interaction as the paramagnetic shielding and, in turn,
(
Cl) of the endohedral Cl
ion correlate inversely with
. Finally, we disclose the synthesis of [PPN][Cl@Si
Y
] (Y=Me, Et, Br) and provide a thorough characterization of these new silafulleranes.</description><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNo9kNFKwzAUQIMobk5ffZT8QGeSm7apbzKmGwwUpuBbSdObGe3S0WyKP-AH-Il-iZnTPeVCzrlcDiHnnA05Y-JSe4dDwQRwKUAdkD5PBU8gz-EwzhIgyVXKe-QkhJfIK8WyY9IDxdIiCn3yOmq9dR5rOsN3F-i9dl24olP_hmHtFnrtWk9bS9fPSJ9oQr8_v-aOChaJNXba_P47Tye6aRfok7E3ehU2TRT9gs5do-2maSLpMZySI6ubgGd_74A83owfRpNkdnc7HV3PEsNZHg_msqoqU3BhRIqyqEArjoZJUFzJrEYrWF6nVmQZFFoVMlNprdFUEjJAa2BAhru9pmtD6NCWq84tdfdRclZuq5XbauW-WhQudsJqUy2x3uP_meAH_RNpSA</recordid><startdate>20240205</startdate><enddate>20240205</enddate><creator>Gasevic, Thomas</creator><creator>Bamberg, Marcel</creator><creator>Wicke, Julius</creator><creator>Bolte, Michael</creator><creator>Virovets, Alexander</creator><creator>Lerner, Hans-Wolfram</creator><creator>Grimme, Stefan</creator><creator>Hansen, Andreas</creator><creator>Wagner, Matthias</creator><creator>Bursch, Markus</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0003-4864-1758</orcidid><orcidid>https://orcid.org/0000-0002-8843-8503</orcidid><orcidid>https://orcid.org/0000-0003-1803-7947</orcidid><orcidid>https://orcid.org/0000-0003-1659-8206</orcidid><orcidid>https://orcid.org/0000-0001-6711-5804</orcidid><orcidid>https://orcid.org/0009-0004-5735-136X</orcidid><orcidid>https://orcid.org/0000-0001-6044-5077</orcidid><orcidid>https://orcid.org/0000-0001-5806-8276</orcidid><orcidid>https://orcid.org/0000-0001-5296-6251</orcidid><orcidid>https://orcid.org/0000-0002-5844-4371</orcidid></search><sort><creationdate>20240205</creationdate><title>Confined Lewis Pairs: Investigation of the X - →Si 20 Interaction in Halogen-Encapsulating Silafulleranes</title><author>Gasevic, Thomas ; Bamberg, Marcel ; Wicke, Julius ; Bolte, Michael ; Virovets, Alexander ; Lerner, Hans-Wolfram ; Grimme, Stefan ; Hansen, Andreas ; Wagner, Matthias ; Bursch, Markus</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c1073-714bbbc912c25e49b3a81ec04381846def207d5f26639a894685daecb4363efc3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Gasevic, Thomas</creatorcontrib><creatorcontrib>Bamberg, Marcel</creatorcontrib><creatorcontrib>Wicke, Julius</creatorcontrib><creatorcontrib>Bolte, Michael</creatorcontrib><creatorcontrib>Virovets, Alexander</creatorcontrib><creatorcontrib>Lerner, Hans-Wolfram</creatorcontrib><creatorcontrib>Grimme, Stefan</creatorcontrib><creatorcontrib>Hansen, Andreas</creatorcontrib><creatorcontrib>Wagner, Matthias</creatorcontrib><creatorcontrib>Bursch, Markus</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Gasevic, Thomas</au><au>Bamberg, Marcel</au><au>Wicke, Julius</au><au>Bolte, Michael</au><au>Virovets, Alexander</au><au>Lerner, Hans-Wolfram</au><au>Grimme, Stefan</au><au>Hansen, Andreas</au><au>Wagner, Matthias</au><au>Bursch, Markus</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Confined Lewis Pairs: Investigation of the X - →Si 20 Interaction in Halogen-Encapsulating Silafulleranes</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew Chem Int Ed Engl</addtitle><date>2024-02-05</date><risdate>2024</risdate><volume>63</volume><issue>6</issue><spage>e202314238</spage><pages>e202314238-</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><abstract>A joint theoretical and experimental study on 32 endohedral silafullerane derivatives [X@Si
Y
]
(X=F-I; Y=F-I, H, Me, Et) and
-[Cl@Si
H
Y
]
(Y=F-I) is presented. First, we evaluated the structure-determining template effect of Cl
in a systematic series of concave silapolyquinane model systems. Second, we investigated the X
→Si
interaction energy (
) as a function of X
and Y and found the largest
values for electron-withdrawing exohedral substituents Y. Given that X
ions can be considered as Lewis bases and empty Si
Y
clusters as Lewis acids, we classify our inseparable host-guest complexes [X@Si
Y
]
as "confined Lewis pairs". Third,
Cl NMR spectroscopy proved to be highly diagnostic for an experimental assessment of the Cl
→Si
interaction as the paramagnetic shielding and, in turn,
(
Cl) of the endohedral Cl
ion correlate inversely with
. Finally, we disclose the synthesis of [PPN][Cl@Si
Y
] (Y=Me, Et, Br) and provide a thorough characterization of these new silafulleranes.</abstract><cop>Germany</cop><pmid>38059423</pmid><doi>10.1002/anie.202314238</doi><orcidid>https://orcid.org/0000-0003-4864-1758</orcidid><orcidid>https://orcid.org/0000-0002-8843-8503</orcidid><orcidid>https://orcid.org/0000-0003-1803-7947</orcidid><orcidid>https://orcid.org/0000-0003-1659-8206</orcidid><orcidid>https://orcid.org/0000-0001-6711-5804</orcidid><orcidid>https://orcid.org/0009-0004-5735-136X</orcidid><orcidid>https://orcid.org/0000-0001-6044-5077</orcidid><orcidid>https://orcid.org/0000-0001-5806-8276</orcidid><orcidid>https://orcid.org/0000-0001-5296-6251</orcidid><orcidid>https://orcid.org/0000-0002-5844-4371</orcidid></addata></record> |
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| title | Confined Lewis Pairs: Investigation of the X - →Si 20 Interaction in Halogen-Encapsulating Silafulleranes |
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