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
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DOI: 10.1002/chem.200700219
Url:
DOI: 10.1002/chem.200700219
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<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>
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<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>
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<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>
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<publicationMeta level="unit" type="article" position="7" status="forIssue"><doi origin="wiley" registered="yes">10.1002/chem.200700219</doi>
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<copyright ownership="publisher">Copyright © 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</copyright>
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<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>
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<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>
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<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>
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<name type="personal"><namePart type="given">J. Jacob</namePart>
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<affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</affiliation>
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<affiliation>Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556–5670, USA, Fax: (+1) 574‐631‐6652</affiliation>
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<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>
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<name type="personal"><namePart type="given">Charles T.</namePart>
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<role><roleTerm type="text">author</roleTerm>
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<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>
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</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>
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<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>
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</extent>
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