Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)
Identifieur interne : 004F07 ( Istex/Corpus ); précédent : 004F06; suivant : 004F08Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)
Auteurs : J. Acob Morris ; Bruce Noll ; Gordon Honeyman ; Charles O'Hara ; Alan Kennedy ; Robert Mulvey ; Kenneth HendersonSource :
- Chemistry – A European Journal [ 0947-6539 ] ; 2007-05-25.
English descriptors
Abstract
Addition of ferrocene to solutions of alkali metal hexamethyldisilazides M(HMDS) in arenes (in which M=Na, K, Rb, Cs) allows the subsequent crystallization of the homologous series of compounds [{(Me3Si)2NM}2⋅ (Cp2Fe)]∞ (1–4). Similar reactions using LiHMDS led to the recrystallization of the starting materials. The crystal structures of 1–4 reveal the formation of one‐dimensional chains composed of dimeric [{M(HMDS)}2] aggregates, which are bridged through neutral ferrocene molecules by η5‐cation–π interactions. In addition, compounds 3 and 4 also contain interchain agostic MC interactions, producing two‐dimensional 44‐nets. Whereas 1 and 2 were prepared from toluene, the syntheses of 3 and 4 required the use of tert‐butylbenzene as the reaction media. The attempted crystallization of 3 and 4 from toluene resulted in formation of the mixed toluene/ferrocene solvated complexes [{(Me3Si)2NM)2}2⋅ (Cp2Fe)x⋅(Tol)y]∞ (in which M=Rb, x=0.6, y=0.8, 5; M=Cs, x=0.5, y=1, 6). The extended solid‐state structures of 5 and 6 are closely related to the 44‐sheets 3 and 4, but are now assembled from a combination of cation–π, agostic, and π–π interactions. The charge‐separated complex [K{(C6H6)2Cr}1.5(Mes)][Mg(HMDS)3] (15) was also structurally characterized and found to adopt an anionic two‐dimensional 63‐network through doubly η3‐coordinated bis(benzene)chromium molecules. DFT calculations at the B3 LYP/6–31G* level of theory indicate that the binding energies of both ferrocene and toluene to the M(HMDS) dimers increases in the sequence Li
Url:
DOI: 10.1002/chem.200700219
Url:
DOI: 10.1002/chem.200700219
Links to Exploration step
ISTEX:32F4862FDFE292D96BC092B9D1B64C73AB5976EBLe document en format XML
<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title xml:lang="en">Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)</title><author><name sortKey="Morris, J Acob" sort="Morris, J Acob" uniqKey="Morris J" first="J. Acob" last="Morris">J. Acob Morris</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</mods:affiliation></affiliation></author><author><name sortKey="Noll, Bruce" sort="Noll, Bruce" uniqKey="Noll B" first="Bruce" last="Noll">Bruce Noll</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</mods:affiliation></affiliation></author><author><name sortKey="Honeyman, Gordon" sort="Honeyman, Gordon" uniqKey="Honeyman G" first="Gordon" last="Honeyman">Gordon Honeyman</name><affiliation><mods:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</mods:affiliation></affiliation></author><author><name sortKey="O Hara, Charles" sort="O Hara, Charles" uniqKey="O Hara C" first="Charles" last="O'Hara">Charles O'Hara</name><affiliation><mods:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</mods:affiliation></affiliation></author><author><name sortKey="Kennedy, Alan" sort="Kennedy, Alan" uniqKey="Kennedy A" first="Alan" last="Kennedy">Alan Kennedy</name><affiliation><mods:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</mods:affiliation></affiliation></author><author><name sortKey="Mulvey, Robert" sort="Mulvey, Robert" uniqKey="Mulvey R" first="Robert" last="Mulvey">Robert Mulvey</name><affiliation><mods:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</mods:affiliation></affiliation></author><author><name sortKey="Henderson, Kenneth" sort="Henderson, Kenneth" uniqKey="Henderson K" first="Kenneth" last="Henderson">Kenneth Henderson</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: khenders@nd.edu</mods:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:32F4862FDFE292D96BC092B9D1B64C73AB5976EB</idno><date when="2007" year="2007">2007</date><idno type="doi">10.1002/chem.200700219</idno><idno type="url">https://api.istex.fr/document/32F4862FDFE292D96BC092B9D1B64C73AB5976EB/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">004F07</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a" type="main" xml:lang="en">Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)</title><author><name sortKey="Morris, J Acob" sort="Morris, J Acob" uniqKey="Morris J" first="J. Acob" last="Morris">J. Acob Morris</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</mods:affiliation></affiliation></author><author><name sortKey="Noll, Bruce" sort="Noll, Bruce" uniqKey="Noll B" first="Bruce" last="Noll">Bruce Noll</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</mods:affiliation></affiliation></author><author><name sortKey="Honeyman, Gordon" sort="Honeyman, Gordon" uniqKey="Honeyman G" first="Gordon" last="Honeyman">Gordon Honeyman</name><affiliation><mods:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</mods:affiliation></affiliation></author><author><name sortKey="O Hara, Charles" sort="O Hara, Charles" uniqKey="O Hara C" first="Charles" last="O'Hara">Charles O'Hara</name><affiliation><mods:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</mods:affiliation></affiliation></author><author><name sortKey="Kennedy, Alan" sort="Kennedy, Alan" uniqKey="Kennedy A" first="Alan" last="Kennedy">Alan Kennedy</name><affiliation><mods:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</mods:affiliation></affiliation></author><author><name sortKey="Mulvey, Robert" sort="Mulvey, Robert" uniqKey="Mulvey R" first="Robert" last="Mulvey">Robert Mulvey</name><affiliation><mods:affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</mods:affiliation></affiliation></author><author><name sortKey="Henderson, Kenneth" sort="Henderson, Kenneth" uniqKey="Henderson K" first="Kenneth" last="Henderson">Kenneth Henderson</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: khenders@nd.edu</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Chemistry – A European Journal</title><title level="j" type="abbrev">Chemistry – A European Journal</title><idno type="ISSN">0947-6539</idno><idno type="eISSN">1521-3765</idno><imprint><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2007-05-25">2007-05-25</date><biblScope unit="volume">13</biblScope><biblScope unit="issue">16</biblScope><biblScope unit="page" from="4418">4418</biblScope><biblScope unit="page" to="4432">4432</biblScope></imprint><idno type="ISSN">0947-6539</idno></series><idno type="istex">32F4862FDFE292D96BC092B9D1B64C73AB5976EB</idno><idno type="DOI">10.1002/chem.200700219</idno><idno type="ArticleID">CHEM200700219</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0947-6539</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>alkali metals</term><term>metallocenes</term><term>noncovalent interactions</term><term>pi interactions</term><term>self‐assembly</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">Addition of ferrocene to solutions of alkali metal hexamethyldisilazides M(HMDS) in arenes (in which M=Na, K, Rb, Cs) allows the subsequent crystallization of the homologous series of compounds [{(Me3Si)2NM}2⋅ (Cp2Fe)]∞ (1–4). Similar reactions using LiHMDS led to the recrystallization of the starting materials. The crystal structures of 1–4 reveal the formation of one‐dimensional chains composed of dimeric [{M(HMDS)}2] aggregates, which are bridged through neutral ferrocene molecules by η5‐cation–π interactions. In addition, compounds 3 and 4 also contain interchain agostic MC interactions, producing two‐dimensional 44‐nets. Whereas 1 and 2 were prepared from toluene, the syntheses of 3 and 4 required the use of tert‐butylbenzene as the reaction media. The attempted crystallization of 3 and 4 from toluene resulted in formation of the mixed toluene/ferrocene solvated complexes [{(Me3Si)2NM)2}2⋅ (Cp2Fe)x⋅(Tol)y]∞ (in which M=Rb, x=0.6, y=0.8, 5; M=Cs, x=0.5, y=1, 6). The extended solid‐state structures of 5 and 6 are closely related to the 44‐sheets 3 and 4, but are now assembled from a combination of cation–π, agostic, and π–π interactions. The charge‐separated complex [K{(C6H6)2Cr}1.5(Mes)][Mg(HMDS)3] (15) was also structurally characterized and found to adopt an anionic two‐dimensional 63‐network through doubly η3‐coordinated bis(benzene)chromium molecules. DFT calculations at the B3 LYP/6–31G* level of theory indicate that the binding energies of both ferrocene and toluene to the M(HMDS) dimers increases in the sequence Li</div> </front></TEI><istex><corpusName>wiley</corpusName><author><json:item><name>J. Jacob Morris</name><affiliations><json:string>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</json:string></affiliations></json:item><json:item><name>Bruce C. Noll Dr.</name><affiliations><json:string>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</json:string></affiliations></json:item><json:item><name>Gordon W. Honeyman Dr.</name><affiliations><json:string>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</json:string></affiliations></json:item><json:item><name>Charles T. O'Hara Dr.</name><affiliations><json:string>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</json:string></affiliations></json:item><json:item><name>Alan R. Kennedy Dr.</name><affiliations><json:string>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</json:string></affiliations></json:item><json:item><name>Robert E. Mulvey Dr.</name><affiliations><json:string>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</json:string></affiliations></json:item><json:item><name>Kenneth W. Henderson Dr.</name><affiliations><json:string>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</json:string><json:string>E-mail: khenders@nd.edu</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>alkali metals</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>metallocenes</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>noncovalent interactions</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>pi interactions</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>self‐assembly</value></json:item></subject><articleId><json:string>CHEM200700219</json:string></articleId><language><json:string>eng</json:string></language><qualityIndicators><score>8</score><pdfVersion>1.3</pdfVersion><pdfPageSize>595 x 842 pts (A4)</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>5</keywordCount><abstractCharCount>1999</abstractCharCount><pdfWordCount>10689</pdfWordCount><pdfCharCount>66695</pdfCharCount><pdfPageCount>15</pdfPageCount><abstractWordCount>283</abstractWordCount></qualityIndicators><title>Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)</title><genre.original><json:string>article</json:string></genre.original><genre><json:string>article</json:string></genre><host><volume>13</volume><publisherId><json:string>CHEM</json:string></publisherId><pages><total>15</total><last>4432</last><first>4418</first></pages><issn><json:string>0947-6539</json:string></issn><issue>16</issue><subject><json:item><value>Full Paper</value></json:item></subject><genre><json:string>journal</json:string></genre><language><json:string>unknown</json:string></language><eissn><json:string>1521-3765</json:string></eissn><title>Chemistry – A European Journal</title><doi><json:string>10.1002/(ISSN)1521-3765</json:string></doi></host><publicationDate>2007</publicationDate><copyrightDate>2007</copyrightDate><doi><json:string>10.1002/chem.200700219</json:string></doi><id>32F4862FDFE292D96BC092B9D1B64C73AB5976EB</id><score>1</score><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/32F4862FDFE292D96BC092B9D1B64C73AB5976EB/fulltext/pdf</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/32F4862FDFE292D96BC092B9D1B64C73AB5976EB/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/32F4862FDFE292D96BC092B9D1B64C73AB5976EB/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><availability><p>WILEY</p></availability><date>2007</date></publicationStmt><notesStmt><note>Petroleum Research Fund - No. 41716-AC3;</note><note>Procter & Gamble</note><note>University of Notre Dame</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a" type="main" xml:lang="en">Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)</title><author><persName><forename type="first">J. Jacob</forename><surname>Morris</surname></persName><affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</affiliation></author><author><persName><forename type="first">Bruce C.</forename><surname>Noll</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</affiliation></author><author><persName><forename type="first">Gordon W.</forename><surname>Honeyman</surname></persName><roleName type="degree">Dr.</roleName><affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</affiliation></author><author><persName><forename type="first">Charles T.</forename><surname>O'Hara</surname></persName><roleName type="degree">Dr.</roleName><affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</affiliation></author><author><persName><forename type="first">Alan R.</forename><surname>Kennedy</surname></persName><roleName type="degree">Dr.</roleName><affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</affiliation></author><author><persName><forename type="first">Robert E.</forename><surname>Mulvey</surname></persName><roleName type="degree">Dr.</roleName><affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</affiliation></author><author><persName><forename type="first">Kenneth W.</forename><surname>Henderson</surname></persName><roleName type="degree">Dr.</roleName><email>khenders@nd.edu</email><affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</affiliation></author></analytic><monogr><title level="j">Chemistry – A European Journal</title><title level="j" type="abbrev">Chemistry – A European Journal</title><idno type="pISSN">0947-6539</idno><idno type="eISSN">1521-3765</idno><idno type="DOI">10.1002/(ISSN)1521-3765</idno><imprint><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2007-05-25"></date><biblScope unit="volume">13</biblScope><biblScope unit="issue">16</biblScope><biblScope unit="page" from="4418">4418</biblScope><biblScope unit="page" to="4432">4432</biblScope></imprint></monogr><idno type="istex">32F4862FDFE292D96BC092B9D1B64C73AB5976EB</idno><idno type="DOI">10.1002/chem.200700219</idno><idno type="ArticleID">CHEM200700219</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2007</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>Addition of ferrocene to solutions of alkali metal hexamethyldisilazides M(HMDS) in arenes (in which M=Na, K, Rb, Cs) allows the subsequent crystallization of the homologous series of compounds [{(Me3Si)2NM}2⋅ (Cp2Fe)]∞ (1–4). Similar reactions using LiHMDS led to the recrystallization of the starting materials. The crystal structures of 1–4 reveal the formation of one‐dimensional chains composed of dimeric [{M(HMDS)}2] aggregates, which are bridged through neutral ferrocene molecules by η5‐cation–π interactions. In addition, compounds 3 and 4 also contain interchain agostic MC interactions, producing two‐dimensional 44‐nets. Whereas 1 and 2 were prepared from toluene, the syntheses of 3 and 4 required the use of tert‐butylbenzene as the reaction media. The attempted crystallization of 3 and 4 from toluene resulted in formation of the mixed toluene/ferrocene solvated complexes [{(Me3Si)2NM)2}2⋅ (Cp2Fe)x⋅(Tol)y]∞ (in which M=Rb, x=0.6, y=0.8, 5; M=Cs, x=0.5, y=1, 6). The extended solid‐state structures of 5 and 6 are closely related to the 44‐sheets 3 and 4, but are now assembled from a combination of cation–π, agostic, and π–π interactions. The charge‐separated complex [K{(C6H6)2Cr}1.5(Mes)][Mg(HMDS)3] (15) was also structurally characterized and found to adopt an anionic two‐dimensional 63‐network through doubly η3‐coordinated bis(benzene)chromium molecules. DFT calculations at the B3 LYP/6–31G* level of theory indicate that the binding energies of both ferrocene and toluene to the M(HMDS) dimers increases in the sequence Li</p> </abstract><abstract xml:lang="en" style="graphical"><p>Directional cation–π interactions: Metallocenes, such as ferrocene and bis(benzene)chromium, can be used in association with pre‐assembled alkali metal aggregates to control the assembly of polymeric materials (an example of which is illustrated here) through directional cation–π interactions.</p></abstract><textClass xml:lang="en"><keywords scheme="keyword"><list><head>keywords</head><item><term>alkali metals</term></item><item><term>metallocenes</term></item><item><term>noncovalent interactions</term></item><item><term>pi interactions</term></item><item><term>self‐assembly</term></item></list></keywords></textClass><textClass><keywords scheme="Journal Subject"><list><head>article-category</head><item><term>Full Paper</term></item></list></keywords></textClass></profileDesc><revisionDesc><change when="2007-02-06">Received</change><change when="2007-05-25">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/32F4862FDFE292D96BC092B9D1B64C73AB5976EB/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Wiley, elements deleted: body"><istex:xmlDeclaration>version="1.0" encoding="UTF-8" standalone="yes"</istex:xmlDeclaration><istex:document><component version="2.0" type="serialArticle" xml:lang="en"><header><publicationMeta level="product"><publisherInfo><publisherName>WILEY‐VCH Verlag</publisherName><publisherLoc>Weinheim</publisherLoc></publisherInfo><doi registered="yes">10.1002/(ISSN)1521-3765</doi><issn type="print">0947-6539</issn><issn type="electronic">1521-3765</issn><idGroup><id type="product" value="CHEM"></id></idGroup><titleGroup><title type="main" xml:lang="en">Chemistry – A European Journal</title><title type="short">Chemistry – A European Journal</title></titleGroup></publicationMeta><publicationMeta level="part" position="160"><doi origin="wiley" registered="yes">10.1002/chem.v13:16</doi><numberingGroup><numbering type="journalVolume" number="13">13</numbering><numbering type="journalIssue">16</numbering></numberingGroup><coverDate startDate="2007-05-25">May 25, 2007</coverDate></publicationMeta><publicationMeta level="unit" type="article" position="7" status="forIssue"><doi origin="wiley" registered="yes">10.1002/chem.200700219</doi><idGroup><id type="unit" value="CHEM200700219"></id></idGroup><countGroup><count type="pageTotal" number="15"></count></countGroup><titleGroup><title type="articleCategory">Full Paper</title><title type="tocHeading1">Full Papers</title></titleGroup><copyright ownership="publisher">Copyright © 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</copyright><eventGroup><event type="manuscriptReceived" date="2007-02-06"></event><event type="firstOnline" date="2007-04-23"></event><event type="publishedOnlineFinalForm" date="2007-05-15"></event><event type="xmlConverted" agent="Converter:JWSART34_TO_WML3G version:2.3.6 mode:FullText source:FullText result:FullText" date="2010-05-18"></event><event type="xmlConverted" agent="Converter:WILEY_ML3G_TO_WILEY_ML3GV2 version:3.8.8" date="2014-01-09"></event><event type="xmlConverted" agent="Converter:WML3G_To_WML3G version:4.1.7 mode:FullText,remove_FC" date="2014-10-15"></event></eventGroup><numberingGroup><numbering type="pageFirst">4418</numbering><numbering type="pageLast">4432</numbering></numberingGroup><objectNameGroup><objectName elementName="figure">Scheme</objectName></objectNameGroup><linkGroup><link type="toTypesetVersion" href="file:CHEM.CHEM200700219.pdf"></link></linkGroup></publicationMeta><contentMeta><countGroup><count type="figureTotal" number="13"></count><count type="tableTotal" number="5"></count><count type="referenceTotal" number="169"></count></countGroup><titleGroup><title type="main" xml:lang="en">Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me<sub>3</sub>Si)<sub>2</sub>NM}<sub>2</sub>⋅(Cp<sub>2</sub>Fe)]<sub>∞</sub> (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)</title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#aa"><personName><givenNames>J. Jacob</givenNames><familyName>Morris</familyName></personName></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Bruce C.</givenNames><familyName>Noll</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au3" creatorRole="author" affiliationRef="#ab"><personName><givenNames>Gordon W.</givenNames><familyName>Honeyman</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au4" creatorRole="author" affiliationRef="#ab"><personName><givenNames>Charles T.</givenNames><familyName>O'Hara</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au5" creatorRole="author" affiliationRef="#ab"><personName><givenNames>Alan R.</givenNames><familyName>Kennedy</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au6" creatorRole="author" affiliationRef="#ab"><personName><givenNames>Robert E.</givenNames><familyName>Mulvey</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au7" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Kenneth W.</givenNames><familyName>Henderson</familyName><degrees>Dr.</degrees></personName><contactDetails><email>khenders@nd.edu</email></contactDetails></creator></creators><affiliationGroup><affiliation xml:id="aa" countryCode="US" type="organization"><unparsedAffiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</unparsedAffiliation></affiliation><affiliation xml:id="ab" countryCode="GB" type="organization"><unparsedAffiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">alkali metals</keyword><keyword xml:id="kwd2">metallocenes</keyword><keyword xml:id="kwd3">noncovalent interactions</keyword><keyword xml:id="kwd4">pi interactions</keyword><keyword xml:id="kwd5">self‐assembly</keyword></keywordGroup><fundingInfo><fundingAgency>Petroleum Research Fund</fundingAgency><fundingNumber>41716-AC3</fundingNumber></fundingInfo><fundingInfo><fundingAgency>Procter & Gamble</fundingAgency></fundingInfo><fundingInfo><fundingAgency>University of Notre Dame</fundingAgency></fundingInfo><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>Addition of ferrocene to solutions of alkali metal hexamethyldisilazides M(HMDS) in arenes (in which M=Na, K, Rb, Cs) allows the subsequent crystallization of the homologous series of compounds [{(Me<sub>3</sub>Si)<sub>2</sub>NM}<sub>2</sub><b>⋅</b> (Cp<sub>2</sub>Fe)]<sub>∞</sub> (<b>1</b>–<b>4</b>). Similar reactions using LiHMDS led to the recrystallization of the starting materials. The crystal structures of <b>1</b>–<b>4</b> reveal the formation of one‐dimensional chains composed of dimeric [{M(HMDS)}<sub>2</sub>] aggregates, which are bridged through neutral ferrocene molecules by η<sup>5</sup>‐cation–π interactions. In addition, compounds <b>3</b> and <b>4</b> also contain interchain agostic MC interactions, producing two‐dimensional 4<sup>4</sup>‐nets. Whereas <b>1</b> and <b>2</b> were prepared from toluene, the syntheses of <b>3</b> and <b>4</b> required the use of <i>tert‐</i>butylbenzene as the reaction media. The attempted crystallization of <b>3</b> and <b>4</b> from toluene resulted in formation of the mixed toluene/ferrocene solvated complexes [{(Me<sub>3</sub>Si)<sub>2</sub>NM)<sub>2</sub>}<sub>2</sub><b>⋅</b> (Cp<sub>2</sub>Fe)<sub><i>x</i></sub><b>⋅</b>(Tol)<sub><i>y</i></sub>]<sub>∞</sub> (in which M=Rb, <i>x</i>=0.6, <i>y</i>=0.8, <b>5</b>; M=Cs, <i>x</i>=0.5, <i>y</i>=1, <b>6</b>). The extended solid‐state structures of <b>5</b> and <b>6</b> are closely related to the 4<sup>4</sup>‐sheets <b>3</b> and <b>4</b>, but are now assembled from a combination of cation–π, agostic, and π–π interactions. The charge‐separated complex [K{(C<sub>6</sub>H<sub>6</sub>)<sub>2</sub>Cr}<sub>1.5</sub>(Mes)][Mg(HMDS)<sub>3</sub>] (<b>15</b>) was also structurally characterized and found to adopt an anionic two‐dimensional 6<sup>3</sup>‐network through doubly η<sup>3</sup>‐coordinated bis(benzene)chromium molecules. DFT calculations at the B3 LYP/6–31G* level of theory indicate that the binding energies of both ferrocene and toluene to the M(HMDS) dimers increases in the sequence Li</p> </abstract><abstract type="graphical" xml:lang="en"><p><b>Directional cation–π interactions</b>: Metallocenes, such as ferrocene and bis(benzene)chromium, can be used in association with pre‐assembled alkali metal aggregates to control the assembly of polymeric materials (an example of which is illustrated here) through directional cation–π interactions.<blockFixed type="graphic"><mediaResourceGroup><mediaResource alt="image" eRights="yes" copyright="WILEY-VCH" href="urn:x-wiley:09476539:media:CHEM200700219:content"></mediaResource><mediaResource alt="thumbnail image" rendition="webLoRes" mimeType="image/gif" href=""></mediaResource><mediaResource alt="original image" rendition="webOriginal" mimeType="image/gif" href=""></mediaResource><mediaResource alt="magnified image" rendition="webHiRes" mimeType="image/gif" href=""></mediaResource></mediaResourceGroup></blockFixed></p></abstract></abstractGroup></contentMeta></header></component></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me</title></titleInfo><name type="personal"><namePart type="given">J. Jacob</namePart><namePart type="family">Morris</namePart><affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Bruce C.</namePart><namePart type="family">Noll</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Gordon W.</namePart><namePart type="family">Honeyman</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Charles T.</namePart><namePart type="family">O'Hara</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Alan R.</namePart><namePart type="family">Kennedy</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Robert E.</namePart><namePart type="family">Mulvey</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland G1 1XL, UK</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Kenneth W.</namePart><namePart type="family">Henderson</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</affiliation><affiliation>E-mail: khenders@nd.edu</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="article" displayLabel="article"></genre><originInfo><publisher>WILEY‐VCH Verlag</publisher><place><placeTerm type="text">Weinheim</placeTerm></place><dateIssued encoding="w3cdtf">2007-05-25</dateIssued><dateCaptured encoding="w3cdtf">2007-02-06</dateCaptured><copyrightDate encoding="w3cdtf">2007</copyrightDate></originInfo><language><languageTerm type="code" authority="rfc3066">en</languageTerm><languageTerm type="code" authority="iso639-2b">eng</languageTerm></language><physicalDescription><internetMediaType>text/html</internetMediaType><extent unit="figures">13</extent><extent unit="tables">5</extent><extent unit="references">169</extent></physicalDescription><abstract lang="en">Addition of ferrocene to solutions of alkali metal hexamethyldisilazides M(HMDS) in arenes (in which M=Na, K, Rb, Cs) allows the subsequent crystallization of the homologous series of compounds [{(Me3Si)2NM}2⋅ (Cp2Fe)]∞ (1–4). Similar reactions using LiHMDS led to the recrystallization of the starting materials. The crystal structures of 1–4 reveal the formation of one‐dimensional chains composed of dimeric [{M(HMDS)}2] aggregates, which are bridged through neutral ferrocene molecules by η5‐cation–π interactions. In addition, compounds 3 and 4 also contain interchain agostic MC interactions, producing two‐dimensional 44‐nets. Whereas 1 and 2 were prepared from toluene, the syntheses of 3 and 4 required the use of tert‐butylbenzene as the reaction media. The attempted crystallization of 3 and 4 from toluene resulted in formation of the mixed toluene/ferrocene solvated complexes [{(Me3Si)2NM)2}2⋅ (Cp2Fe)x⋅(Tol)y]∞ (in which M=Rb, x=0.6, y=0.8, 5; M=Cs, x=0.5, y=1, 6). The extended solid‐state structures of 5 and 6 are closely related to the 44‐sheets 3 and 4, but are now assembled from a combination of cation–π, agostic, and π–π interactions. The charge‐separated complex [K{(C6H6)2Cr}1.5(Mes)][Mg(HMDS)3] (15) was also structurally characterized and found to adopt an anionic two‐dimensional 63‐network through doubly η3‐coordinated bis(benzene)chromium molecules. DFT calculations at the B3 LYP/6–31G* level of theory indicate that the binding energies of both ferrocene and toluene to the M(HMDS) dimers increases in the sequence Li</abstract> <abstract type="graphical" lang="en">Directional cation–π interactions: Metallocenes, such as ferrocene and bis(benzene)chromium, can be used in association with pre‐assembled alkali metal aggregates to control the assembly of polymeric materials (an example of which is illustrated here) through directional cation–π interactions.</abstract><note type="funding">Petroleum Research Fund - No. 41716-AC3; </note><note type="funding">Procter & Gamble</note><note type="funding">University of Notre Dame</note><subject lang="en"><genre>keywords</genre><topic>alkali metals</topic><topic>metallocenes</topic><topic>noncovalent interactions</topic><topic>pi interactions</topic><topic>self‐assembly</topic></subject><relatedItem type="host"><titleInfo><title>Chemistry – A European Journal</title></titleInfo><titleInfo type="abbreviated"><title>Chemistry – A European Journal</title></titleInfo><genre type="journal">journal</genre><subject><genre>article-category</genre><topic>Full Paper</topic></subject><identifier type="ISSN">0947-6539</identifier><identifier type="eISSN">1521-3765</identifier><identifier type="DOI">10.1002/(ISSN)1521-3765</identifier><identifier type="PublisherID">CHEM</identifier><part><date>2007</date><detail type="volume"><caption>vol.</caption><number>13</number></detail><detail type="issue"><caption>no.</caption><number>16</number></detail><extent unit="pages"><start>4418</start><end>4432</end><total>15</total></extent></part></relatedItem><identifier type="istex">32F4862FDFE292D96BC092B9D1B64C73AB5976EB</identifier><identifier type="DOI">10.1002/chem.200700219</identifier><identifier type="ArticleID">CHEM200700219</identifier><accessCondition type="use and reproduction" contentType="copyright">Copyright © 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</accessCondition><recordInfo><recordContentSource>WILEY</recordContentSource><recordOrigin>WILEY‐VCH Verlag</recordOrigin></recordInfo></mods></metadata><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Ticri/CIDE/explor/HapticV1/Data/Istex/Corpus
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 004F07 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Istex/Corpus/biblio.hfd -nk 004F07 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Ticri/CIDE
|area= HapticV1
|flux= Istex
|étape= Corpus
|type= RBID
|clé= ISTEX:32F4862FDFE292D96BC092B9D1B64C73AB5976EB
|texte= Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)
}}
| This area was generated with Dilib version V0.6.23. |  |