Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds: The [Me₂Si] bridge as a site for metallocene functionalization

[Me₂Si(CpMe²)₂]W(H)Cl is obtained via reaction of WCl₆ with a mixture of [Me₂Si(CpMe²)₂]Li₂ and NaBH₄, from which the dichloride [Me₂Si(CpMe²)₂]WCl₂ is obtained via treatment with CHCl₃. [Me₂Si(CpMe²)₂]WCl₂ provides a means to access other ansa tungstenocene compounds, such as [Me₂Si(CpMe²)₂]WH₂, [M...

Full description

Saved in:
Bibliographic Details
Published in:Proceedings of the National Academy of Sciences - PNAS 2008-08, Vol.105 (32), p.11060-11065
Main Authors: Zachmanoglou, Cary E, Lee, Hyosun, Jang, Seung Ho, Pang, Keliang, Parkin, Gerard
Format: Article
Language:English
Subjects:
Ansae
Atoms
Carbon
Carbon - chemistry
Chemical bonding
Chemical bonds
Chemical compounds
Chemical reactions
Hydrides
Isomers
Ligands
Metals - chemistry
Molecular structure
Pentanes
Physical Sciences
Silicon
Silicon - chemistry
Silicon Compounds - chemical synthesis
Silicon Compounds - chemistry
X ray diffraction
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
cited_by cdi_FETCH-LOGICAL-c523t-594e864807db6ded295a988994535d6fa0914a0815e42e7f6f97d466ce94f0c03
cites cdi_FETCH-LOGICAL-c523t-594e864807db6ded295a988994535d6fa0914a0815e42e7f6f97d466ce94f0c03
container_end_page 11065
container_issue 32
container_start_page 11060
container_title Proceedings of the National Academy of Sciences - PNAS
container_volume 105
creator Zachmanoglou, Cary E
Lee, Hyosun
Jang, Seung Ho
Pang, Keliang
Parkin, Gerard
description [Me₂Si(CpMe²)₂]W(H)Cl is obtained via reaction of WCl₆ with a mixture of [Me₂Si(CpMe²)₂]Li₂ and NaBH₄, from which the dichloride [Me₂Si(CpMe²)₂]WCl₂ is obtained via treatment with CHCl₃. [Me₂Si(CpMe²)₂]WCl₂ provides a means to access other ansa tungstenocene compounds, such as [Me₂Si(CpMe²)₂]WH₂, [Me₂Si(CpMe²)₂]WMe₂, and [Me₂Si(CpMe²)₂]WCO. Of most interest, the reactions of [Me₂Si(CpMe²)₂]W(H)Cl with organolithium reagents do not yield simple ansa tungstenocene derivatives. Specifically, the reactions of [Me₂Si(CpMe²)₂]W(H)Cl with MeLi, BunLi, or PhLi result in the formation of mixed-ring tungstenocene compounds resulting from C-Si cleavage and functionalization of the ansa bridge, namely (CpMe²)(η⁵,κ¹-C₅H₂Me₂SiMe₂CH₂)WH, (CpMe²)[η⁵,κ¹-C₅H₂Me₂Si(Me)(Bun)CH₂]WH, and (CpMe²)[η⁵,κ¹-C₅H₂Me₂SiMe₂(C₆H₄)]WH, respectively. In contrast to the C-Si cleavage achieved by MeLi, BunLi, and PhLi, the ansa bridge of [Me₂Si(CpMe²)₂]W(H)Cl is inert to ButLi and the product obtained is the fulvene ("tuck-in") complex [Me₂Si(CpMe²)(η⁶-C₅MeH₂CH₂)]WH derived from dehydrohalogenation.
doi_str_mv 10.1073/pnas.0803089105
format article
fullrecord <record><control><sourceid>jstor_proqu</sourceid><recordid>TN_cdi_proquest_miscellaneous_69422521</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><jstor_id>25463292</jstor_id><sourcerecordid>25463292</sourcerecordid><originalsourceid>FETCH-LOGICAL-c523t-594e864807db6ded295a988994535d6fa0914a0815e42e7f6f97d466ce94f0c03</originalsourceid><addsrcrecordid>eNqFkk1vFCEcxidGY2v17EklHkw8TAsMrx5Mmo1vSY2HbU_GEHYGtmxYWIFp1GNPfk4_iUx301UvHggk_9_zhIeHpnmM4DGCvDvZBJ2PoYAdFBJBeqc5RFCilhEJ7zaHEGLeCoLJQfMg5xWEUFIB7zcHSLCOMsEPm59z510fQzvTaREDqGsAvTf6Si8NSEb3xcWQQbTgNGQNyhiWuZgQexMM6ON6E8cw5Ffg_NKAzx_Nr-vrufsCFskNVa8z0CC7YoCNCaxN0d5vlXYMN87aux96Ojxs7lnts3m024-ai7dvzmfv27NP7z7MTs_anuKutFQSIxgRkA8LNpgBS6qlEFIS2tGBWV3jEw0FooZgwy2zkg-Esd5IYmEPu6Pm9dZ3My7WZqiXKUl7tUlurdN3FbVTf0-Cu1TLeKUwRQxjVA1e7AxS_DqaXNTa5d54r4OJY1ZMEozpDfj8H3AVx1QTZ4Uh6jgiiFfoZAv1KeacjL29CYJqqlhNFat9xVXx9M8Ae37XaQXADpiUezuqOqwQgmx6hJf_QZQdvS_mW6nsky27yiWmWxhTwjoscZ0_286tjkovk8vqYj4FrL8NU8559xteptCA</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>201371417</pqid></control><display><type>article</type><title>Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds: The [Me₂Si] bridge as a site for metallocene functionalization</title><source>JSTOR Archival Journals and Primary Sources Collection</source><source>PubMed Central</source><creator>Zachmanoglou, Cary E ; Lee, Hyosun ; Jang, Seung Ho ; Pang, Keliang ; Parkin, Gerard</creator><creatorcontrib>Zachmanoglou, Cary E ; Lee, Hyosun ; Jang, Seung Ho ; Pang, Keliang ; Parkin, Gerard</creatorcontrib><description>[Me₂Si(CpMe²)₂]W(H)Cl is obtained via reaction of WCl₆ with a mixture of [Me₂Si(CpMe²)₂]Li₂ and NaBH₄, from which the dichloride [Me₂Si(CpMe²)₂]WCl₂ is obtained via treatment with CHCl₃. [Me₂Si(CpMe²)₂]WCl₂ provides a means to access other ansa tungstenocene compounds, such as [Me₂Si(CpMe²)₂]WH₂, [Me₂Si(CpMe²)₂]WMe₂, and [Me₂Si(CpMe²)₂]WCO. Of most interest, the reactions of [Me₂Si(CpMe²)₂]W(H)Cl with organolithium reagents do not yield simple ansa tungstenocene derivatives. Specifically, the reactions of [Me₂Si(CpMe²)₂]W(H)Cl with MeLi, BunLi, or PhLi result in the formation of mixed-ring tungstenocene compounds resulting from C-Si cleavage and functionalization of the ansa bridge, namely (CpMe²)(η⁵,κ¹-C₅H₂Me₂SiMe₂CH₂)WH, (CpMe²)[η⁵,κ¹-C₅H₂Me₂Si(Me)(Bun)CH₂]WH, and (CpMe²)[η⁵,κ¹-C₅H₂Me₂SiMe₂(C₆H₄)]WH, respectively. In contrast to the C-Si cleavage achieved by MeLi, BunLi, and PhLi, the ansa bridge of [Me₂Si(CpMe²)₂]W(H)Cl is inert to ButLi and the product obtained is the fulvene ("tuck-in") complex [Me₂Si(CpMe²)(η⁶-C₅MeH₂CH₂)]WH derived from dehydrohalogenation.</description><identifier>ISSN: 0027-8424</identifier><identifier>EISSN: 1091-6490</identifier><identifier>DOI: 10.1073/pnas.0803089105</identifier><identifier>PMID: 18635687</identifier><language>eng</language><publisher>United States: National Academy of Sciences</publisher><subject>Ansae ; Atoms ; Carbon ; Carbon - chemistry ; Chemical bonding ; Chemical bonds ; Chemical compounds ; Chemical reactions ; Hydrides ; Isomers ; Ligands ; Metals - chemistry ; Molecular structure ; Pentanes ; Physical Sciences ; Silicon ; Silicon - chemistry ; Silicon Compounds - chemical synthesis ; Silicon Compounds - chemistry ; X ray diffraction</subject><ispartof>Proceedings of the National Academy of Sciences - PNAS, 2008-08, Vol.105 (32), p.11060-11065</ispartof><rights>Copyright 2008 The National Academy of Sciences of the United States of America</rights><rights>Copyright National Academy of Sciences Aug 12, 2008</rights><rights>2008 by The National Academy of Sciences of the USA</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c523t-594e864807db6ded295a988994535d6fa0914a0815e42e7f6f97d466ce94f0c03</citedby><cites>FETCH-LOGICAL-c523t-594e864807db6ded295a988994535d6fa0914a0815e42e7f6f97d466ce94f0c03</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Uhttp://www.pnas.org/content/105/32.cover.gif</thumbnail><linktopdf>$$Uhttps://www.jstor.org/stable/pdf/25463292$$EPDF$$P50$$Gjstor$$H</linktopdf><linktohtml>$$Uhttps://www.jstor.org/stable/25463292$$EHTML$$P50$$Gjstor$$H</linktohtml><link.rule.ids>230,314,727,780,784,885,27924,27925,53791,53793,58238,58471</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/18635687$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Zachmanoglou, Cary E</creatorcontrib><creatorcontrib>Lee, Hyosun</creatorcontrib><creatorcontrib>Jang, Seung Ho</creatorcontrib><creatorcontrib>Pang, Keliang</creatorcontrib><creatorcontrib>Parkin, Gerard</creatorcontrib><title>Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds: The [Me₂Si] bridge as a site for metallocene functionalization</title><title>Proceedings of the National Academy of Sciences - PNAS</title><addtitle>Proc Natl Acad Sci U S A</addtitle><description>[Me₂Si(CpMe²)₂]W(H)Cl is obtained via reaction of WCl₆ with a mixture of [Me₂Si(CpMe²)₂]Li₂ and NaBH₄, from which the dichloride [Me₂Si(CpMe²)₂]WCl₂ is obtained via treatment with CHCl₃. [Me₂Si(CpMe²)₂]WCl₂ provides a means to access other ansa tungstenocene compounds, such as [Me₂Si(CpMe²)₂]WH₂, [Me₂Si(CpMe²)₂]WMe₂, and [Me₂Si(CpMe²)₂]WCO. Of most interest, the reactions of [Me₂Si(CpMe²)₂]W(H)Cl with organolithium reagents do not yield simple ansa tungstenocene derivatives. Specifically, the reactions of [Me₂Si(CpMe²)₂]W(H)Cl with MeLi, BunLi, or PhLi result in the formation of mixed-ring tungstenocene compounds resulting from C-Si cleavage and functionalization of the ansa bridge, namely (CpMe²)(η⁵,κ¹-C₅H₂Me₂SiMe₂CH₂)WH, (CpMe²)[η⁵,κ¹-C₅H₂Me₂Si(Me)(Bun)CH₂]WH, and (CpMe²)[η⁵,κ¹-C₅H₂Me₂SiMe₂(C₆H₄)]WH, respectively. In contrast to the C-Si cleavage achieved by MeLi, BunLi, and PhLi, the ansa bridge of [Me₂Si(CpMe²)₂]W(H)Cl is inert to ButLi and the product obtained is the fulvene ("tuck-in") complex [Me₂Si(CpMe²)(η⁶-C₅MeH₂CH₂)]WH derived from dehydrohalogenation.</description><subject>Ansae</subject><subject>Atoms</subject><subject>Carbon</subject><subject>Carbon - chemistry</subject><subject>Chemical bonding</subject><subject>Chemical bonds</subject><subject>Chemical compounds</subject><subject>Chemical reactions</subject><subject>Hydrides</subject><subject>Isomers</subject><subject>Ligands</subject><subject>Metals - chemistry</subject><subject>Molecular structure</subject><subject>Pentanes</subject><subject>Physical Sciences</subject><subject>Silicon</subject><subject>Silicon - chemistry</subject><subject>Silicon Compounds - chemical synthesis</subject><subject>Silicon Compounds - chemistry</subject><subject>X ray diffraction</subject><issn>0027-8424</issn><issn>1091-6490</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2008</creationdate><recordtype>article</recordtype><recordid>eNqFkk1vFCEcxidGY2v17EklHkw8TAsMrx5Mmo1vSY2HbU_GEHYGtmxYWIFp1GNPfk4_iUx301UvHggk_9_zhIeHpnmM4DGCvDvZBJ2PoYAdFBJBeqc5RFCilhEJ7zaHEGLeCoLJQfMg5xWEUFIB7zcHSLCOMsEPm59z510fQzvTaREDqGsAvTf6Si8NSEb3xcWQQbTgNGQNyhiWuZgQexMM6ON6E8cw5Ffg_NKAzx_Nr-vrufsCFskNVa8z0CC7YoCNCaxN0d5vlXYMN87aux96Ojxs7lnts3m024-ai7dvzmfv27NP7z7MTs_anuKutFQSIxgRkA8LNpgBS6qlEFIS2tGBWV3jEw0FooZgwy2zkg-Esd5IYmEPu6Pm9dZ3My7WZqiXKUl7tUlurdN3FbVTf0-Cu1TLeKUwRQxjVA1e7AxS_DqaXNTa5d54r4OJY1ZMEozpDfj8H3AVx1QTZ4Uh6jgiiFfoZAv1KeacjL29CYJqqlhNFat9xVXx9M8Ae37XaQXADpiUezuqOqwQgmx6hJf_QZQdvS_mW6nsky27yiWmWxhTwjoscZ0_286tjkovk8vqYj4FrL8NU8559xteptCA</recordid><startdate>20080812</startdate><enddate>20080812</enddate><creator>Zachmanoglou, Cary E</creator><creator>Lee, Hyosun</creator><creator>Jang, Seung Ho</creator><creator>Pang, Keliang</creator><creator>Parkin, Gerard</creator><general>National Academy of Sciences</general><general>National Acad Sciences</general><scope>FBQ</scope><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>7QG</scope><scope>7QL</scope><scope>7QP</scope><scope>7QR</scope><scope>7SN</scope><scope>7SS</scope><scope>7T5</scope><scope>7TK</scope><scope>7TM</scope><scope>7TO</scope><scope>7U9</scope><scope>8FD</scope><scope>C1K</scope><scope>FR3</scope><scope>H94</scope><scope>M7N</scope><scope>P64</scope><scope>RC3</scope><scope>7X8</scope><scope>5PM</scope></search><sort><creationdate>20080812</creationdate><title>Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds: The [Me₂Si] bridge as a site for metallocene functionalization</title><author>Zachmanoglou, Cary E ; Lee, Hyosun ; Jang, Seung Ho ; Pang, Keliang ; Parkin, Gerard</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c523t-594e864807db6ded295a988994535d6fa0914a0815e42e7f6f97d466ce94f0c03</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2008</creationdate><topic>Ansae</topic><topic>Atoms</topic><topic>Carbon</topic><topic>Carbon - chemistry</topic><topic>Chemical bonding</topic><topic>Chemical bonds</topic><topic>Chemical compounds</topic><topic>Chemical reactions</topic><topic>Hydrides</topic><topic>Isomers</topic><topic>Ligands</topic><topic>Metals - chemistry</topic><topic>Molecular structure</topic><topic>Pentanes</topic><topic>Physical Sciences</topic><topic>Silicon</topic><topic>Silicon - chemistry</topic><topic>Silicon Compounds - chemical synthesis</topic><topic>Silicon Compounds - chemistry</topic><topic>X ray diffraction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Zachmanoglou, Cary E</creatorcontrib><creatorcontrib>Lee, Hyosun</creatorcontrib><creatorcontrib>Jang, Seung Ho</creatorcontrib><creatorcontrib>Pang, Keliang</creatorcontrib><creatorcontrib>Parkin, Gerard</creatorcontrib><collection>AGRIS</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Animal Behavior Abstracts</collection><collection>Bacteriology Abstracts (Microbiology B)</collection><collection>Calcium &amp; Calcified Tissue Abstracts</collection><collection>Chemoreception Abstracts</collection><collection>Ecology Abstracts</collection><collection>Entomology Abstracts (Full archive)</collection><collection>Immunology Abstracts</collection><collection>Neurosciences Abstracts</collection><collection>Nucleic Acids Abstracts</collection><collection>Oncogenes and Growth Factors Abstracts</collection><collection>Virology and AIDS Abstracts</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Engineering Research Database</collection><collection>AIDS and Cancer Research Abstracts</collection><collection>Algology Mycology and Protozoology Abstracts (Microbiology C)</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>Genetics Abstracts</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Proceedings of the National Academy of Sciences - PNAS</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Zachmanoglou, Cary E</au><au>Lee, Hyosun</au><au>Jang, Seung Ho</au><au>Pang, Keliang</au><au>Parkin, Gerard</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds: The [Me₂Si] bridge as a site for metallocene functionalization</atitle><jtitle>Proceedings of the National Academy of Sciences - PNAS</jtitle><addtitle>Proc Natl Acad Sci U S A</addtitle><date>2008-08-12</date><risdate>2008</risdate><volume>105</volume><issue>32</issue><spage>11060</spage><epage>11065</epage><pages>11060-11065</pages><issn>0027-8424</issn><eissn>1091-6490</eissn><abstract>[Me₂Si(CpMe²)₂]W(H)Cl is obtained via reaction of WCl₆ with a mixture of [Me₂Si(CpMe²)₂]Li₂ and NaBH₄, from which the dichloride [Me₂Si(CpMe²)₂]WCl₂ is obtained via treatment with CHCl₃. [Me₂Si(CpMe²)₂]WCl₂ provides a means to access other ansa tungstenocene compounds, such as [Me₂Si(CpMe²)₂]WH₂, [Me₂Si(CpMe²)₂]WMe₂, and [Me₂Si(CpMe²)₂]WCO. Of most interest, the reactions of [Me₂Si(CpMe²)₂]W(H)Cl with organolithium reagents do not yield simple ansa tungstenocene derivatives. Specifically, the reactions of [Me₂Si(CpMe²)₂]W(H)Cl with MeLi, BunLi, or PhLi result in the formation of mixed-ring tungstenocene compounds resulting from C-Si cleavage and functionalization of the ansa bridge, namely (CpMe²)(η⁵,κ¹-C₅H₂Me₂SiMe₂CH₂)WH, (CpMe²)[η⁵,κ¹-C₅H₂Me₂Si(Me)(Bun)CH₂]WH, and (CpMe²)[η⁵,κ¹-C₅H₂Me₂SiMe₂(C₆H₄)]WH, respectively. In contrast to the C-Si cleavage achieved by MeLi, BunLi, and PhLi, the ansa bridge of [Me₂Si(CpMe²)₂]W(H)Cl is inert to ButLi and the product obtained is the fulvene ("tuck-in") complex [Me₂Si(CpMe²)(η⁶-C₅MeH₂CH₂)]WH derived from dehydrohalogenation.</abstract><cop>United States</cop><pub>National Academy of Sciences</pub><pmid>18635687</pmid><doi>10.1073/pnas.0803089105</doi><tpages>6</tpages><oa>free_for_read</oa></addata></record>
fulltext fulltext
identifier ISSN: 0027-8424
ispartof Proceedings of the National Academy of Sciences - PNAS, 2008-08, Vol.105 (32), p.11060-11065
issn 0027-8424
1091-6490
language eng
recordid cdi_proquest_miscellaneous_69422521
source JSTOR Archival Journals and Primary Sources Collection; PubMed Central
subjects Ansae
Atoms
Carbon
Carbon - chemistry
Chemical bonding
Chemical bonds
Chemical compounds
Chemical reactions
Hydrides
Isomers
Ligands
Metals - chemistry
Molecular structure
Pentanes
Physical Sciences
Silicon
Silicon - chemistry
Silicon Compounds - chemical synthesis
Silicon Compounds - chemistry
X ray diffraction
title Silicon-Carbon bond cleavage reactions of Ansa tungstenocene compounds: The [Me₂Si] bridge as a site for metallocene functionalization
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-29T19%3A34%3A39IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-jstor_proqu&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Silicon-Carbon%20bond%20cleavage%20reactions%20of%20Ansa%20tungstenocene%20compounds:%20The%20%5BMe%E2%82%82Si%5D%20bridge%20as%20a%20site%20for%20metallocene%20functionalization&rft.jtitle=Proceedings%20of%20the%20National%20Academy%20of%20Sciences%20-%20PNAS&rft.au=Zachmanoglou,%20Cary%20E&rft.date=2008-08-12&rft.volume=105&rft.issue=32&rft.spage=11060&rft.epage=11065&rft.pages=11060-11065&rft.issn=0027-8424&rft.eissn=1091-6490&rft_id=info:doi/10.1073/pnas.0803089105&rft_dat=%3Cjstor_proqu%3E25463292%3C/jstor_proqu%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-c523t-594e864807db6ded295a988994535d6fa0914a0815e42e7f6f97d466ce94f0c03%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=201371417&rft_id=info:pmid/18635687&rft_jstor_id=25463292&rfr_iscdi=true