The Versatility of Pentalene Coordination to Transition Metals: A Density Functional Theory Investigation
Identifieur interne : 004016 ( Istex/Corpus ); précédent : 004015; suivant : 004017The Versatility of Pentalene Coordination to Transition Metals: A Density Functional Theory Investigation
Auteurs : Saïda Bendjaballah ; Samia Kahlal ; Karine Costuas ; Emile Bévillon ; Jean Ves SaillardSource :
- Chemistry – A European Journal [ 0947-6539 ] ; 2006-02-20.
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Abstract
DFT calculations with full geometry optimization have been carried out on a series of real and hypothetical compounds of the type [CpM(C8H6)], [(CO)3M(C8H6)], [M(C8H6)2], [(CpM)2(C8H6)], [{(CO)3M}2(C8H6)], and [M2(C8H6)2] (M=transition metal). The bonding in all the currently known compounds is rationalized, as well as in the (so far) hypothetical stable complexes. Depending on the electron count and the nature of the metal(s), η2 (predicted), η3, η5, η8, or intermediate coordination modes can be adopted. In the case of the mononuclear species, the most favored closed‐shell electron counts are 18 and 16 metal valence electrons (MVE). In the case of the dinuclear species, an electron count of 34 MVEs is most favored. However, other electron counts can be stabilized, especially in the case of dinuclear complexes. Coordinated pentalene should most often be considered as formally being a dianion, but sometimes as a neutral ligand. In the former case it can behave as an aromatic species made of two equivalent fused rings, as a C5 aromatic ring connected to an allylic anion, or even as two allylic anions bridged by a C7C8 double bond. In the latter case, it can behave as a bond‐alternating cyclic polyene or as a C5 aromatic ring connected to an allylic cation.
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DOI: 10.1002/chem.200500765
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saillard@univ‐rennes1.fr</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="2006-02-20">2006-02-20</date><biblScope unit="volume">12</biblScope><biblScope unit="issue">7</biblScope><biblScope unit="page" from="2048">2048</biblScope><biblScope unit="page" to="2065">2065</biblScope></imprint><idno type="ISSN">0947-6539</idno></series><idno type="istex">7572A0DB5038E453DC32109619B85561CC5271F1</idno><idno type="DOI">10.1002/chem.200500765</idno><idno type="ArticleID">CHEM200500765</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0947-6539</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>coordination 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The bonding in all the currently known compounds is rationalized, as well as in the (so far) hypothetical stable complexes. Depending on the electron count and the nature of the metal(s), η2 (predicted), η3, η5, η8, or intermediate coordination modes can be adopted. In the case of the mononuclear species, the most favored closed‐shell electron counts are 18 and 16 metal valence electrons (MVE). In the case of the dinuclear species, an electron count of 34 MVEs is most favored. However, other electron counts can be stabilized, especially in the case of dinuclear complexes. Coordinated pentalene should most often be considered as formally being a dianion, but sometimes as a neutral ligand. In the former case it can behave as an aromatic species made of two equivalent fused rings, as a C5 aromatic ring connected to an allylic anion, or even as two allylic anions bridged by a C7C8 double bond. 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The bonding in all the currently known compounds is rationalized, as well as in the (so far) hypothetical stable complexes. Depending on the electron count and the nature of the metal(s), η2 (predicted), η3, η5, η8, or intermediate coordination modes can be adopted. In the case of the mononuclear species, the most favored closed‐shell electron counts are 18 and 16 metal valence electrons (MVE). In the case of the dinuclear species, an electron count of 34 MVEs is most favored. However, other electron counts can be stabilized, especially in the case of dinuclear complexes. Coordinated pentalene should most often be considered as formally being a dianion, but sometimes as a neutral ligand. In the former case it can behave as an aromatic species made of two equivalent fused rings, as a C5 aromatic ring connected to an allylic anion, or even as two allylic anions bridged by a C7C8 double bond. In the latter case, it can behave as a bond‐alternating cyclic polyene or as a C5 aromatic ring connected to an allylic cation.</p></abstract><abstract xml:lang="en" style="graphical"><p>Club 16 to 34: Depending on the electron count and the nature of the metal(s), η2 (predicted), η3, η5, η8, or intermediate coordination modes can be adopted by pentalene (some examples are shown here). For the mononuclear species, the most favored closed‐shell electron counts are 18 and 16 metal valence electrons (MVEs), whereas for the dinuclear species, an electron count of 34 MVEs is most favored.</p></abstract><textClass xml:lang="en"><keywords scheme="keyword"><list><head>keywords</head><item><term>coordination modes</term></item><item><term>density functional calculations</term></item><item><term>electron count</term></item><item><term>pentalene</term></item><item><term>transition metals</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="2005-07-03">Received</change><change when="2006-02-20">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/7572A0DB5038E453DC32109619B85561CC5271F1/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="70"><doi origin="wiley" registered="yes">10.1002/chem.v12:7</doi><numberingGroup><numbering type="journalVolume" number="12">12</numbering><numbering type="journalIssue">7</numbering></numberingGroup><coverDate startDate="2006-02-20">February 20, 2006</coverDate></publicationMeta><publicationMeta level="unit" type="article" position="22" status="forIssue"><doi origin="wiley" registered="yes">10.1002/chem.200500765</doi><idGroup><id type="unit" value="CHEM200500765"></id></idGroup><countGroup><count type="pageTotal" number="18"></count></countGroup><titleGroup><title type="articleCategory">Full Paper</title></titleGroup><copyright ownership="publisher">Copyright © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</copyright><eventGroup><event type="manuscriptReceived" date="2005-07-03"></event><event type="firstOnline" date="2005-12-15"></event><event type="publishedOnlineFinalForm" date="2006-02-10"></event><event type="xmlConverted" agent="Converter:JWSART34_TO_WML3G version:2.3.6 mode:FullText source:FullText result:FullText mathml2tex" 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">2048</numbering><numbering type="pageLast">2065</numbering></numberingGroup><objectNameGroup><objectName elementName="figure">Scheme</objectName></objectNameGroup><linkGroup><link type="toTypesetVersion" href="file:CHEM.CHEM2048.pdf"></link></linkGroup></publicationMeta><contentMeta><countGroup><count type="figureTotal" number="25"></count><count type="tableTotal" number="10"></count><count type="referenceTotal" number="109"></count></countGroup><titleGroup><title type="main" xml:lang="en">The Versatility of Pentalene Coordination to Transition Metals: A Density Functional Theory Investigation</title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Saïda</givenNames><familyName>Bendjaballah</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Samia</givenNames><familyName>Kahlal</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au3" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Karine</givenNames><familyName>Costuas</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au4" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Emile</givenNames><familyName>Bévillon</familyName></personName></creator><creator xml:id="au5" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Jean‐Yves</givenNames><familyName>Saillard</familyName><degrees>Prof.</degrees></personName><contactDetails><email normalForm="saillard@univ-rennes1.fr">saillard@univ‐rennes1.fr</email></contactDetails></creator></creators><affiliationGroup><affiliation xml:id="aa" countryCode="FR" type="organization"><unparsedAffiliation>Laboratoire de Chimie du Solide et Inorganique Moléculaire, UMR CNRS 6511, Institut de Chimie de Rennes, Université de Rennes 1, 35042 Rennes Cedex, France, Fax: (+33) 223‐236‐840</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">coordination modes</keyword><keyword xml:id="kwd2">density functional calculations</keyword><keyword xml:id="kwd3">electron count</keyword><keyword xml:id="kwd4">pentalene</keyword><keyword xml:id="kwd5">transition metals</keyword></keywordGroup><supportingInformation><p>Supporting information for this article is available on the WWW under <url href="http://www.wiley-vch.de/contents/jc_2111/2006/f500765_s.pdf">http://www.wiley‐vch.de/contents/jc_2111/2006/f500765_s.pdf</url> or from the author.</p></supportingInformation><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>DFT calculations with full geometry optimization have been carried out on a series of real and hypothetical compounds of the type [CpM(C<sub>8</sub>H<sub>6</sub>)], [(CO)<sub>3</sub>M(C<sub>8</sub>H<sub>6</sub>)], [M(C<sub>8</sub>H<sub>6</sub>)<sub>2</sub>], [(CpM)<sub>2</sub>(C<sub>8</sub>H<sub>6</sub>)], [{(CO)<sub>3</sub>M}<sub>2</sub>(C<sub>8</sub>H<sub>6</sub>)], and [M<sub>2</sub>(C<sub>8</sub>H<sub>6</sub>)<sub>2</sub>] (M=transition metal). The bonding in all the currently known compounds is rationalized, as well as in the (so far) hypothetical stable complexes. Depending on the electron count and the nature of the metal(s), η<sup>2</sup> (predicted), η<sup>3</sup>, η<sup>5</sup>, η<sup>8</sup>, or intermediate coordination modes can be adopted. In the case of the mononuclear species, the most favored closed‐shell electron counts are 18 and 16 metal valence electrons (MVE). In the case of the dinuclear species, an electron count of 34 MVEs is most favored. However, other electron counts can be stabilized, especially in the case of dinuclear complexes. Coordinated pentalene should most often be considered as formally being a dianion, but sometimes as a neutral ligand. In the former case it can behave as an aromatic species made of two equivalent fused rings, as a C<sub>5</sub> aromatic ring connected to an allylic anion, or even as two allylic anions bridged by a C7C8 double bond. In the latter case, it can behave as a bond‐alternating cyclic polyene or as a C<sub>5</sub> aromatic ring connected to an allylic cation.</p></abstract><abstract type="graphical" xml:lang="en"><p><b>Club 16 to 34</b>: Depending on the electron count and the nature of the metal(s), η<sup>2</sup> (predicted), η<sup>3</sup>, η<sup>5</sup>, η<sup>8</sup>, or intermediate coordination modes can be adopted by pentalene (some examples are shown here). For the mononuclear species, the most favored closed‐shell electron counts are 18 and 16 metal valence electrons (MVEs), whereas for the dinuclear species, an electron count of 34 MVEs is most favored.<blockFixed type="graphic"><mediaResourceGroup><mediaResource alt="image" eRights="yes" copyright="WILEY-VCH" href="urn:x-wiley:09476539:media:CHEM200500765: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>The Versatility of Pentalene Coordination to Transition Metals: A Density Functional Theory Investigation</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>The Versatility of Pentalene Coordination to Transition Metals: A Density Functional Theory Investigation</title></titleInfo><name type="personal"><namePart type="given">Saïda</namePart><namePart type="family">Bendjaballah</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire de Chimie du Solide et Inorganique Moléculaire, UMR CNRS 6511, Institut de Chimie de Rennes, Université de Rennes 1, 35042 Rennes Cedex, France, Fax: (+33) 223‐236‐840</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Samia</namePart><namePart type="family">Kahlal</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire de Chimie du Solide et Inorganique Moléculaire, UMR CNRS 6511, Institut de Chimie de Rennes, Université de Rennes 1, 35042 Rennes Cedex, France, Fax: (+33) 223‐236‐840</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Karine</namePart><namePart type="family">Costuas</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire de Chimie du Solide et Inorganique Moléculaire, UMR CNRS 6511, Institut de Chimie de Rennes, Université de Rennes 1, 35042 Rennes Cedex, France, Fax: (+33) 223‐236‐840</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Emile</namePart><namePart type="family">Bévillon</namePart><affiliation>Laboratoire de Chimie du Solide et Inorganique Moléculaire, UMR CNRS 6511, Institut de Chimie de Rennes, Université de Rennes 1, 35042 Rennes Cedex, France, Fax: (+33) 223‐236‐840</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Jean‐Yves</namePart><namePart type="family">Saillard</namePart><namePart type="termsOfAddress">Prof.</namePart><affiliation>Laboratoire de Chimie du Solide et Inorganique Moléculaire, UMR CNRS 6511, Institut de Chimie de Rennes, Université de Rennes 1, 35042 Rennes Cedex, France, Fax: (+33) 223‐236‐840</affiliation><affiliation>E-mail: saillard@univ‐rennes1.fr</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">2006-02-20</dateIssued><dateCaptured encoding="w3cdtf">2005-07-03</dateCaptured><copyrightDate encoding="w3cdtf">2006</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">25</extent><extent unit="tables">10</extent><extent unit="references">109</extent></physicalDescription><abstract lang="en">DFT calculations with full geometry optimization have been carried out on a series of real and hypothetical compounds of the type [CpM(C8H6)], [(CO)3M(C8H6)], [M(C8H6)2], [(CpM)2(C8H6)], [{(CO)3M}2(C8H6)], and [M2(C8H6)2] (M=transition metal). The bonding in all the currently known compounds is rationalized, as well as in the (so far) hypothetical stable complexes. Depending on the electron count and the nature of the metal(s), η2 (predicted), η3, η5, η8, or intermediate coordination modes can be adopted. In the case of the mononuclear species, the most favored closed‐shell electron counts are 18 and 16 metal valence electrons (MVE). In the case of the dinuclear species, an electron count of 34 MVEs is most favored. However, other electron counts can be stabilized, especially in the case of dinuclear complexes. Coordinated pentalene should most often be considered as formally being a dianion, but sometimes as a neutral ligand. In the former case it can behave as an aromatic species made of two equivalent fused rings, as a C5 aromatic ring connected to an allylic anion, or even as two allylic anions bridged by a C7C8 double bond. In the latter case, it can behave as a bond‐alternating cyclic polyene or as a C5 aromatic ring connected to an allylic cation.</abstract><abstract type="graphical" lang="en">Club 16 to 34: Depending on the electron count and the nature of the metal(s), η2 (predicted), η3, η5, η8, or intermediate coordination modes can be adopted by pentalene (some examples are shown here). For the mononuclear species, the most favored closed‐shell electron counts are 18 and 16 metal valence electrons (MVEs), whereas for the dinuclear species, an electron count of 34 MVEs is most favored.</abstract><subject lang="en"><genre>keywords</genre><topic>coordination modes</topic><topic>density functional calculations</topic><topic>electron count</topic><topic>pentalene</topic><topic>transition metals</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><note type="content"> Supporting information for this article is available on the WWW under http://www.wiley‐vch.de/contents/jc_2111/2006/f500765_s.pdf or from the author.</note><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>2006</date><detail type="volume"><caption>vol.</caption><number>12</number></detail><detail type="issue"><caption>no.</caption><number>7</number></detail><extent unit="pages"><start>2048</start><end>2065</end><total>18</total></extent></part></relatedItem><identifier type="istex">7572A0DB5038E453DC32109619B85561CC5271F1</identifier><identifier type="DOI">10.1002/chem.200500765</identifier><identifier type="ArticleID">CHEM200500765</identifier><accessCondition type="use and reproduction" contentType="copyright">Copyright © 2006 WILEY‐VCH Verlag GmbH & Co. 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