Functionalization of Zeolite ZSM-5 by Hydrosilylation and Acetone Coupling: Synthesis, MAS NMR, and Theory
We report a two-step postsynthetic functionalization reaction of zeolite HZSM-5 that proceeds with high selectivity at room temperature. In the first step the framework acid sites of the zeolite are reacted with phenylsilane to replace the acidic proton with a hydrosilyl (−SiH3) group covalently lin...
Gespeichert in:
| Veröffentlicht in: | The journal of physical chemistry. B 2006-08, Vol.110 (30), p.14598-14603 |
|---|---|
| Hauptverfasser: | , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 14603 |
|---|---|
| container_issue | 30 |
| container_start_page | 14598 |
| container_title | The journal of physical chemistry. B |
| container_volume | 110 |
| creator | Abubakar, Saifudin M Lee, Jeffrey C Marcus, David M Ehresmann, Justin O Haw, James F |
| description | We report a two-step postsynthetic functionalization reaction of zeolite HZSM-5 that proceeds with high selectivity at room temperature. In the first step the framework acid sites of the zeolite are reacted with phenylsilane to replace the acidic proton with a hydrosilyl (−SiH3) group covalently linked to the framework. This group readily couples to acetone in a second step to form a framework-bound hydrosilyl isopropyl ether that is thermally stable at 473 K, but decomposes in the presence of moisture. We characterized these reactions using 29Si, 1H, and 13C MAS NMR, as appropriate. Theoretical modeling using density functional theory and cluster models of the zeolite acid site confirmed that both steps were exothermic and provided theoretical chemical shift values in excellent agreement with experiment. |
| doi_str_mv | 10.1021/jp061791f |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_68683540</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>68683540</sourcerecordid><originalsourceid>FETCH-LOGICAL-a351t-72f72e1fb07fe2b193f6444cd1fcc475e5179cbd12b50929b3e81fc5542ad8a93</originalsourceid><addsrcrecordid>eNpt0c1O3DAQB3CrApWP9tAXQL4UCWnT2k7sJNxWK5aPsm3Fbi9cLMcZg7fZeIkTiXDiymvyJJhmRS8cLI80P401fyP0hZJvlDD6fbkmgqY5NR_QLuWMROGkW5taUCJ20J73S0IYZ5n4iHaoyETOBdlFq2lX69a6WlX2Qb0W2Bl8Da6yLeDr-SziuOjxWV82ztuqrwaj6hKPNbSuBjxx3bqy9c3x8-MTnvd1ewve-hGejef45-xq9A8vbsE1_Se0bVTl4fPm3kd_pieLyVl0-ev0fDK-jFTMaRulzKQMqClIaoAVNI-NSJJEl9RonaQceNhWFyVlBSc5y4sYstDiPGGqzFQe76PDYe66cXcd-FaurNdQVaoG13kZ1s9inpAAjwaow3q-ASPXjV2pppeUyNds5Vu2wR5shnbFCsr_chNmANEArG_h_q2vmr9SpHHK5eL3XIrp5CL7McvkVfBfB6-0l0vXNeET_DsPvwCB1o_b</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>68683540</pqid></control><display><type>article</type><title>Functionalization of Zeolite ZSM-5 by Hydrosilylation and Acetone Coupling: Synthesis, MAS NMR, and Theory</title><source>American Chemical Society Journals</source><creator>Abubakar, Saifudin M ; Lee, Jeffrey C ; Marcus, David M ; Ehresmann, Justin O ; Haw, James F</creator><creatorcontrib>Abubakar, Saifudin M ; Lee, Jeffrey C ; Marcus, David M ; Ehresmann, Justin O ; Haw, James F</creatorcontrib><description>We report a two-step postsynthetic functionalization reaction of zeolite HZSM-5 that proceeds with high selectivity at room temperature. In the first step the framework acid sites of the zeolite are reacted with phenylsilane to replace the acidic proton with a hydrosilyl (−SiH3) group covalently linked to the framework. This group readily couples to acetone in a second step to form a framework-bound hydrosilyl isopropyl ether that is thermally stable at 473 K, but decomposes in the presence of moisture. We characterized these reactions using 29Si, 1H, and 13C MAS NMR, as appropriate. Theoretical modeling using density functional theory and cluster models of the zeolite acid site confirmed that both steps were exothermic and provided theoretical chemical shift values in excellent agreement with experiment.</description><identifier>ISSN: 1520-6106</identifier><identifier>EISSN: 1520-5207</identifier><identifier>DOI: 10.1021/jp061791f</identifier><identifier>PMID: 16869560</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>The journal of physical chemistry. B, 2006-08, Vol.110 (30), p.14598-14603</ispartof><rights>Copyright © 2006 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a351t-72f72e1fb07fe2b193f6444cd1fcc475e5179cbd12b50929b3e81fc5542ad8a93</citedby><cites>FETCH-LOGICAL-a351t-72f72e1fb07fe2b193f6444cd1fcc475e5179cbd12b50929b3e81fc5542ad8a93</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jp061791f$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jp061791f$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/16869560$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Abubakar, Saifudin M</creatorcontrib><creatorcontrib>Lee, Jeffrey C</creatorcontrib><creatorcontrib>Marcus, David M</creatorcontrib><creatorcontrib>Ehresmann, Justin O</creatorcontrib><creatorcontrib>Haw, James F</creatorcontrib><title>Functionalization of Zeolite ZSM-5 by Hydrosilylation and Acetone Coupling: Synthesis, MAS NMR, and Theory</title><title>The journal of physical chemistry. B</title><addtitle>J. Phys. Chem. B</addtitle><description>We report a two-step postsynthetic functionalization reaction of zeolite HZSM-5 that proceeds with high selectivity at room temperature. In the first step the framework acid sites of the zeolite are reacted with phenylsilane to replace the acidic proton with a hydrosilyl (−SiH3) group covalently linked to the framework. This group readily couples to acetone in a second step to form a framework-bound hydrosilyl isopropyl ether that is thermally stable at 473 K, but decomposes in the presence of moisture. We characterized these reactions using 29Si, 1H, and 13C MAS NMR, as appropriate. Theoretical modeling using density functional theory and cluster models of the zeolite acid site confirmed that both steps were exothermic and provided theoretical chemical shift values in excellent agreement with experiment.</description><issn>1520-6106</issn><issn>1520-5207</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2006</creationdate><recordtype>article</recordtype><recordid>eNpt0c1O3DAQB3CrApWP9tAXQL4UCWnT2k7sJNxWK5aPsm3Fbi9cLMcZg7fZeIkTiXDiymvyJJhmRS8cLI80P401fyP0hZJvlDD6fbkmgqY5NR_QLuWMROGkW5taUCJ20J73S0IYZ5n4iHaoyETOBdlFq2lX69a6WlX2Qb0W2Bl8Da6yLeDr-SziuOjxWV82ztuqrwaj6hKPNbSuBjxx3bqy9c3x8-MTnvd1ewve-hGejef45-xq9A8vbsE1_Se0bVTl4fPm3kd_pieLyVl0-ev0fDK-jFTMaRulzKQMqClIaoAVNI-NSJJEl9RonaQceNhWFyVlBSc5y4sYstDiPGGqzFQe76PDYe66cXcd-FaurNdQVaoG13kZ1s9inpAAjwaow3q-ASPXjV2pppeUyNds5Vu2wR5shnbFCsr_chNmANEArG_h_q2vmr9SpHHK5eL3XIrp5CL7McvkVfBfB6-0l0vXNeET_DsPvwCB1o_b</recordid><startdate>20060803</startdate><enddate>20060803</enddate><creator>Abubakar, Saifudin M</creator><creator>Lee, Jeffrey C</creator><creator>Marcus, David M</creator><creator>Ehresmann, Justin O</creator><creator>Haw, James F</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20060803</creationdate><title>Functionalization of Zeolite ZSM-5 by Hydrosilylation and Acetone Coupling: Synthesis, MAS NMR, and Theory</title><author>Abubakar, Saifudin M ; Lee, Jeffrey C ; Marcus, David M ; Ehresmann, Justin O ; Haw, James F</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a351t-72f72e1fb07fe2b193f6444cd1fcc475e5179cbd12b50929b3e81fc5542ad8a93</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2006</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Abubakar, Saifudin M</creatorcontrib><creatorcontrib>Lee, Jeffrey C</creatorcontrib><creatorcontrib>Marcus, David M</creatorcontrib><creatorcontrib>Ehresmann, Justin O</creatorcontrib><creatorcontrib>Haw, James F</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>The journal of physical chemistry. B</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Abubakar, Saifudin M</au><au>Lee, Jeffrey C</au><au>Marcus, David M</au><au>Ehresmann, Justin O</au><au>Haw, James F</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Functionalization of Zeolite ZSM-5 by Hydrosilylation and Acetone Coupling: Synthesis, MAS NMR, and Theory</atitle><jtitle>The journal of physical chemistry. B</jtitle><addtitle>J. Phys. Chem. B</addtitle><date>2006-08-03</date><risdate>2006</risdate><volume>110</volume><issue>30</issue><spage>14598</spage><epage>14603</epage><pages>14598-14603</pages><issn>1520-6106</issn><eissn>1520-5207</eissn><abstract>We report a two-step postsynthetic functionalization reaction of zeolite HZSM-5 that proceeds with high selectivity at room temperature. In the first step the framework acid sites of the zeolite are reacted with phenylsilane to replace the acidic proton with a hydrosilyl (−SiH3) group covalently linked to the framework. This group readily couples to acetone in a second step to form a framework-bound hydrosilyl isopropyl ether that is thermally stable at 473 K, but decomposes in the presence of moisture. We characterized these reactions using 29Si, 1H, and 13C MAS NMR, as appropriate. Theoretical modeling using density functional theory and cluster models of the zeolite acid site confirmed that both steps were exothermic and provided theoretical chemical shift values in excellent agreement with experiment.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>16869560</pmid><doi>10.1021/jp061791f</doi><tpages>6</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1520-6106 |
| ispartof | The journal of physical chemistry. B, 2006-08, Vol.110 (30), p.14598-14603 |
| issn | 1520-6106 1520-5207 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_68683540 |
| source | American Chemical Society Journals |
| title | Functionalization of Zeolite ZSM-5 by Hydrosilylation and Acetone Coupling: Synthesis, MAS NMR, and Theory |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-02T00%3A17%3A34IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Functionalization%20of%20Zeolite%20ZSM-5%20by%20Hydrosilylation%20and%20Acetone%20Coupling:%E2%80%89%20Synthesis,%20MAS%20NMR,%20and%20Theory&rft.jtitle=The%20journal%20of%20physical%20chemistry.%20B&rft.au=Abubakar,%20Saifudin%20M&rft.date=2006-08-03&rft.volume=110&rft.issue=30&rft.spage=14598&rft.epage=14603&rft.pages=14598-14603&rft.issn=1520-6106&rft.eissn=1520-5207&rft_id=info:doi/10.1021/jp061791f&rft_dat=%3Cproquest_cross%3E68683540%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=68683540&rft_id=info:pmid/16869560&rfr_iscdi=true |