Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters
Identifieur interne : 000647 ( Istex/Corpus ); précédent : 000646; suivant : 000648Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters
Auteurs : Mustapha Bencharif ; Olivier Cador ; Hélène Cattey ; Alexander Ebner ; Jean-François Halet ; Samia Kahlal ; Walter Meier ; Yves Mugnier ; Jean-Yves Saillard ; Patrick Schwarz ; Fatima Zohra Trodi ; Joachim Wachter ; Manfred ZabelSource :
- European Journal of Inorganic Chemistry [ 1434-1948 ] ; 2008-04.
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Abstract
Extended investigations of the reaction sequence [Cp′2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp′ = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3]–/[3]2–/[3]3–/[3]4–/[3]5– regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3]– containing salts form with PPh3AuCl or dppe decomposition products like [(PPh3)2Au][CoCl3PPh3] or [Co(CO)2dppe]2(μ‐Te). A neutral cluster comprising the Co@Co8(μ4‐Te)6 core formed in the reaction of [Cp*2Nb(CO)2][Co11Te7(CO)10] with PPh3AuCl, which gave [Co9Te6(CO)4(PPh3)4] (4) after oxidative cluster degradation and CO substitution. 4 was characterized by X‐ray crystallography. DFT calculations carried out on all members of the [3]n (n = +1 to –5) family and on related species indicate that there is no significant Jahn–Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][3] show that the ground state of [3]– is a spin triplet with spins interacting antiferromagnetically in a 1D space.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
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DOI: 10.1002/ejic.200701350
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uniqKey="Cattey H" first="Hélène" last="Cattey">Hélène Cattey</name><affiliation><mods:affiliation>Institut de Chimie Moléculaire de l'Université de Bourgogne ICMUB‐UMR CNRS 5260, Faculté des Sciences Mirande, Université de Bourgogne, 21100 Dijon, France</mods:affiliation></affiliation></author><author><name sortKey="Ebner, Alexander" sort="Ebner, Alexander" uniqKey="Ebner A" first="Alexander" last="Ebner">Alexander Ebner</name><affiliation><mods:affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</mods:affiliation></affiliation></author><author><name sortKey="Halet, Jean Rancois" sort="Halet, Jean Rancois" uniqKey="Halet J" first="Jean-François" last="Halet">Jean-François Halet</name><affiliation><mods:affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Kahlal, Samia" sort="Kahlal, Samia" uniqKey="Kahlal S" first="Samia" last="Kahlal">Samia Kahlal</name><affiliation><mods:affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Meier, Walter" sort="Meier, Walter" uniqKey="Meier W" first="Walter" last="Meier">Walter Meier</name><affiliation><mods:affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</mods:affiliation></affiliation></author><author><name sortKey="Mugnier, Yves" sort="Mugnier, Yves" uniqKey="Mugnier Y" first="Yves" last="Mugnier">Yves Mugnier</name><affiliation><mods:affiliation>Institut de Chimie Moléculaire de l'Université de Bourgogne ICMUB‐UMR CNRS 5260, Faculté des Sciences Mirande, Université de Bourgogne, 21100 Dijon, France</mods:affiliation></affiliation></author><author><name sortKey="Saillard, Jean Ves" sort="Saillard, Jean Ves" uniqKey="Saillard J" first="Jean-Yves" last="Saillard">Jean-Yves Saillard</name><affiliation><mods:affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Schwarz, Patrick" sort="Schwarz, Patrick" uniqKey="Schwarz P" first="Patrick" last="Schwarz">Patrick Schwarz</name><affiliation><mods:affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</mods:affiliation></affiliation></author><author><name sortKey="Trodi, Fatima Zohra" sort="Trodi, Fatima Zohra" uniqKey="Trodi F" first="Fatima Zohra" last="Trodi">Fatima Zohra Trodi</name><affiliation><mods:affiliation>Departement de Chimie, Faculté des Sciences Exactes, Université Mentouri‐Constantine, 25000 Constantine, Algeria</mods:affiliation></affiliation><affiliation><mods:affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Wachter, Joachim" sort="Wachter, Joachim" uniqKey="Wachter J" first="Joachim" last="Wachter">Joachim Wachter</name><affiliation><mods:affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: joachim.wachter@chemie.uni‐regensburg.de</mods:affiliation></affiliation></author><author><name sortKey="Zabel, Manfred" sort="Zabel, Manfred" uniqKey="Zabel M" first="Manfred" last="Zabel">Manfred Zabel</name><affiliation><mods:affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">European Journal of Inorganic Chemistry</title><title level="j" type="abbrev">Eur. J. Inorg. Chem.</title><idno type="ISSN">1434-1948</idno><idno type="eISSN">1099-0682</idno><imprint><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2008-04">2008-04</date><biblScope unit="volume">2008</biblScope><biblScope unit="issue">12</biblScope><biblScope unit="page" from="1959">1959</biblScope><biblScope unit="page" to="1968">1968</biblScope></imprint><idno type="ISSN">1434-1948</idno></series><idno type="istex">A3880727306C37B2B0BB6632BAD51CE31A841019</idno><idno type="DOI">10.1002/ejic.200701350</idno><idno type="ArticleID">EJIC200701350</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">1434-1948</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Cluster</term><term>Cobalt</term><term>Electrochemistry</term><term>Electronic structure</term><term>Tellurium</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract">Extended investigations of the reaction sequence [Cp′2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp′ = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3]–/[3]2–/[3]3–/[3]4–/[3]5– regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3]– containing salts form with PPh3AuCl or dppe decomposition products like [(PPh3)2Au][CoCl3PPh3] or [Co(CO)2dppe]2(μ‐Te). A neutral cluster comprising the Co@Co8(μ4‐Te)6 core formed in the reaction of [Cp*2Nb(CO)2][Co11Te7(CO)10] with PPh3AuCl, which gave [Co9Te6(CO)4(PPh3)4] (4) after oxidative cluster degradation and CO substitution. 4 was characterized by X‐ray crystallography. DFT calculations carried out on all members of the [3]n (n = +1 to –5) family and on related species indicate that there is no significant Jahn–Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][3] show that the ground state of [3]– is a spin triplet with spins interacting antiferromagnetically in a 1D space.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</div></front></TEI><istex><corpusName>wiley</corpusName><author><json:item><name>Mustapha Bencharif</name><affiliations><json:string>Departement de Chimie, Faculté des Sciences Exactes, Université Mentouri‐Constantine, 25000 Constantine, Algeria</json:string></affiliations></json:item><json:item><name>Olivier Cador</name><affiliations><json:string>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</json:string></affiliations></json:item><json:item><name>Hélène Cattey</name><affiliations><json:string>Institut de Chimie Moléculaire de l'Université de Bourgogne ICMUB‐UMR CNRS 5260, Faculté des Sciences Mirande, Université de Bourgogne, 21100 Dijon, France</json:string></affiliations></json:item><json:item><name>Alexander Ebner</name><affiliations><json:string>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</json:string></affiliations></json:item><json:item><name>Jean‐François Halet</name><affiliations><json:string>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</json:string></affiliations></json:item><json:item><name>Samia Kahlal</name><affiliations><json:string>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</json:string></affiliations></json:item><json:item><name>Walter Meier</name><affiliations><json:string>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</json:string></affiliations></json:item><json:item><name>Yves Mugnier</name><affiliations><json:string>Institut de Chimie Moléculaire de l'Université de Bourgogne ICMUB‐UMR CNRS 5260, Faculté des Sciences Mirande, Université de Bourgogne, 21100 Dijon, France</json:string></affiliations></json:item><json:item><name>Jean‐Yves Saillard</name><affiliations><json:string>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</json:string></affiliations></json:item><json:item><name>Patrick Schwarz</name><affiliations><json:string>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</json:string></affiliations></json:item><json:item><name>Fatima Zohra Trodi</name><affiliations><json:string>Departement de Chimie, Faculté des Sciences Exactes, Université Mentouri‐Constantine, 25000 Constantine, Algeria</json:string><json:string>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</json:string></affiliations></json:item><json:item><name>Joachim Wachter</name><affiliations><json:string>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</json:string><json:string>E-mail: joachim.wachter@chemie.uni‐regensburg.de</json:string></affiliations></json:item><json:item><name>Manfred Zabel</name><affiliations><json:string>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>Cobalt</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Tellurium</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Cluster</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Electrochemistry</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Electronic structure</value></json:item></subject><articleId><json:string>EJIC200701350</json:string></articleId><language><json:string>eng</json:string></language><originalGenre><json:string>bookReview</json:string></originalGenre><abstract>A series of cobalt‐centered hexacapped clusters containg the Co9(μ4‐Te)6L8 core is described in which the metal electron count (MVE) ranges from 120 to 126 MVE. Structural, electrochemical (including the [Cp*2Nb(CO)2]+ cation) and theoretical investigations prove the remarkable electron‐sponge behavior of this class of compounds.</abstract><qualityIndicators><score>7.556</score><pdfVersion>1.3</pdfVersion><pdfPageSize>595 x 794 pts</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>5</keywordCount><abstractCharCount>1524</abstractCharCount><pdfWordCount>6398</pdfWordCount><pdfCharCount>39981</pdfCharCount><pdfPageCount>10</pdfPageCount><abstractWordCount>213</abstractWordCount></qualityIndicators><title>Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters</title><genre><json:string>book-reviews</json:string></genre><host><volume>2008</volume><publisherId><json:string>EJIC</json:string></publisherId><pages><total>10</total><last>1968</last><first>1959</first></pages><issn><json:string>1434-1948</json:string></issn><issue>12</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>1099-0682</json:string></eissn><title>European Journal of Inorganic Chemistry</title><doi><json:string>10.1002/(ISSN)1099-0682c</json:string></doi></host><publicationDate>2008</publicationDate><copyrightDate>2008</copyrightDate><doi><json:string>10.1002/ejic.200701350</json:string></doi><id>A3880727306C37B2B0BB6632BAD51CE31A841019</id><score>0.10283564</score><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/A3880727306C37B2B0BB6632BAD51CE31A841019/fulltext/pdf</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/A3880727306C37B2B0BB6632BAD51CE31A841019/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/A3880727306C37B2B0BB6632BAD51CE31A841019/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><availability><p>Copyright © 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</p></availability><date>2008</date></publicationStmt><notesStmt><note>Deutsche Forschungsgemeinschaft (DFG)</note><note>French‐Algerian Comité Mixte d'Evaluation et de Perspective - No. CMEP/02 MD U552;</note><note>Algerian Government</note><note>Institut Universitaire de France (IUF)</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a" type="main" xml:lang="en">Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters</title><author xml:id="author-1"><persName><forename type="first">Mustapha</forename><surname>Bencharif</surname></persName><affiliation>Departement de Chimie, Faculté des Sciences Exactes, Université Mentouri‐Constantine, 25000 Constantine, Algeria</affiliation></author><author xml:id="author-2"><persName><forename type="first">Olivier</forename><surname>Cador</surname></persName><affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</affiliation></author><author xml:id="author-3"><persName><forename type="first">Hélène</forename><surname>Cattey</surname></persName><affiliation>Institut de Chimie Moléculaire de l'Université de Bourgogne ICMUB‐UMR CNRS 5260, Faculté des Sciences Mirande, Université de Bourgogne, 21100 Dijon, France</affiliation></author><author xml:id="author-4"><persName><forename type="first">Alexander</forename><surname>Ebner</surname></persName><affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</affiliation></author><author xml:id="author-5"><persName><forename type="first">Jean‐François</forename><surname>Halet</surname></persName><affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</affiliation></author><author xml:id="author-6"><persName><forename type="first">Samia</forename><surname>Kahlal</surname></persName><affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</affiliation></author><author xml:id="author-7"><persName><forename type="first">Walter</forename><surname>Meier</surname></persName><affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</affiliation></author><author xml:id="author-8"><persName><forename type="first">Yves</forename><surname>Mugnier</surname></persName><affiliation>Institut de Chimie Moléculaire de l'Université de Bourgogne ICMUB‐UMR CNRS 5260, Faculté des Sciences Mirande, Université de Bourgogne, 21100 Dijon, France</affiliation></author><author xml:id="author-9"><persName><forename type="first">Jean‐Yves</forename><surname>Saillard</surname></persName><affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</affiliation></author><author xml:id="author-10"><persName><forename type="first">Patrick</forename><surname>Schwarz</surname></persName><affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</affiliation></author><author xml:id="author-11"><persName><forename type="first">Fatima Zohra</forename><surname>Trodi</surname></persName><affiliation>Departement de Chimie, Faculté des Sciences Exactes, Université Mentouri‐Constantine, 25000 Constantine, Algeria</affiliation><affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</affiliation></author><author xml:id="author-12"><persName><forename type="first">Joachim</forename><surname>Wachter</surname></persName><email>joachim.wachter@chemie.uni‐regensburg.de</email><affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</affiliation></author><author xml:id="author-13"><persName><forename type="first">Manfred</forename><surname>Zabel</surname></persName><affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</affiliation></author></analytic><monogr><title level="j">European Journal of Inorganic Chemistry</title><title level="j" type="abbrev">Eur. J. Inorg. Chem.</title><idno type="pISSN">1434-1948</idno><idno type="eISSN">1099-0682</idno><idno type="DOI">10.1002/(ISSN)1099-0682c</idno><imprint><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2008-04"></date><biblScope unit="volume">2008</biblScope><biblScope unit="issue">12</biblScope><biblScope unit="page" from="1959">1959</biblScope><biblScope unit="page" to="1968">1968</biblScope></imprint></monogr><idno type="istex">A3880727306C37B2B0BB6632BAD51CE31A841019</idno><idno type="DOI">10.1002/ejic.200701350</idno><idno type="ArticleID">EJIC200701350</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2008</date></creation><langUsage><language ident="en">en</language></langUsage><abstract><p>Extended investigations of the reaction sequence [Cp′2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp′ = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3]–/[3]2–/[3]3–/[3]4–/[3]5– regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3]– containing salts form with PPh3AuCl or dppe decomposition products like [(PPh3)2Au][CoCl3PPh3] or [Co(CO)2dppe]2(μ‐Te). A neutral cluster comprising the Co@Co8(μ4‐Te)6 core formed in the reaction of [Cp*2Nb(CO)2][Co11Te7(CO)10] with PPh3AuCl, which gave [Co9Te6(CO)4(PPh3)4] (4) after oxidative cluster degradation and CO substitution. 4 was characterized by X‐ray crystallography. DFT calculations carried out on all members of the [3]n (n = +1 to –5) family and on related species indicate that there is no significant Jahn–Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][3] show that the ground state of [3]– is a spin triplet with spins interacting antiferromagnetically in a 1D space.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</p></abstract><abstract xml:lang="en" style="graphical"><p>A series of cobalt‐centered hexacapped clusters containg the Co9(μ4‐Te)6L8 core is described in which the metal electron count (MVE) ranges from 120 to 126 MVE. Structural, electrochemical (including the [Cp*2Nb(CO)2]+ cation) and theoretical investigations prove the remarkable electron‐sponge behavior of this class of compounds.</p></abstract><textClass xml:lang="en"><keywords scheme="keyword"><list><head>keywords</head><item><term>Cobalt</term></item><item><term>Tellurium</term></item><item><term>Cluster</term></item><item><term>Electrochemistry</term></item><item><term>Electronic structure</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="2007-12-18">Received</change><change when="2008-04">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/A3880727306C37B2B0BB6632BAD51CE31A841019/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)1099-0682c</doi><issn type="print">1434-1948</issn><issn type="electronic">1099-0682</issn><idGroup><id type="product" value="EJIC"></id></idGroup><titleGroup><title type="main" xml:lang="en" sort="EUROPEAN JOURNAL OF INORGANIC CHEMISTRY">European Journal of Inorganic Chemistry</title><title type="short">Eur. J. Inorg. Chem.</title></titleGroup></publicationMeta><publicationMeta level="part" position="120"><doi origin="wiley" registered="yes">10.1002/ejic.v2008:12</doi><numberingGroup><numbering type="journalVolume" number="2008">2008</numbering><numbering type="journalIssue">12</numbering></numberingGroup><coverDate startDate="2008-04">April 2008</coverDate></publicationMeta><publicationMeta level="unit" type="bookReview" position="5" status="forIssue"><doi origin="wiley" registered="yes">10.1002/ejic.200701350</doi><idGroup><id type="unit" value="EJIC200701350"></id></idGroup><countGroup><count type="pageTotal" number="10"></count></countGroup><titleGroup><title type="articleCategory">Full Paper</title><title type="tocHeading1">Full Papers</title></titleGroup><copyright ownership="publisher">Copyright © 2008 WILEY‐VCH Verlag GmbH & Co. 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number="11"></count><count type="tableTotal" number="3"></count><count type="referenceTotal" number="25"></count></countGroup><titleGroup><title type="main" xml:lang="en">Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co<sub>9</sub>Te<sub>6</sub>(CO)<sub>8</sub> Clusters</title><title type="short" xml:lang="en">Cobalt‐Centered Cubic Co<sub>9</sub>Te<sub>6</sub>(CO)<sub>8</sub> Clusters</title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Mustapha</givenNames><familyName>Bencharif</familyName></personName></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#af2"><personName><givenNames>Olivier</givenNames><familyName>Cador</familyName></personName></creator><creator xml:id="au3" creatorRole="author" affiliationRef="#af3"><personName><givenNames>Hélène</givenNames><familyName>Cattey</familyName></personName></creator><creator xml:id="au4" creatorRole="author" affiliationRef="#af4"><personName><givenNames>Alexander</givenNames><familyName>Ebner</familyName></personName></creator><creator xml:id="au5" creatorRole="author" affiliationRef="#af2"><personName><givenNames>Jean‐François</givenNames><familyName>Halet</familyName></personName></creator><creator xml:id="au6" creatorRole="author" affiliationRef="#af2"><personName><givenNames>Samia</givenNames><familyName>Kahlal</familyName></personName></creator><creator xml:id="au7" creatorRole="author" affiliationRef="#af4"><personName><givenNames>Walter</givenNames><familyName>Meier</familyName></personName></creator><creator xml:id="au8" creatorRole="author" affiliationRef="#af3"><personName><givenNames>Yves</givenNames><familyName>Mugnier</familyName></personName></creator><creator xml:id="au9" creatorRole="author" affiliationRef="#af2"><personName><givenNames>Jean‐Yves</givenNames><familyName>Saillard</familyName></personName></creator><creator xml:id="au10" creatorRole="author" affiliationRef="#af4"><personName><givenNames>Patrick</givenNames><familyName>Schwarz</familyName></personName></creator><creator xml:id="au11" creatorRole="author" affiliationRef="#af1 #af2"><personName><givenNames>Fatima Zohra</givenNames><familyName>Trodi</familyName></personName></creator><creator xml:id="au12" creatorRole="author" affiliationRef="#af4"><personName><givenNames>Joachim</givenNames><familyName>Wachter</familyName></personName><contactDetails><email normalForm="joachim.wachter@chemie.uni-regensburg.de">joachim.wachter@chemie.uni‐regensburg.de</email></contactDetails></creator><creator xml:id="au13" creatorRole="author" affiliationRef="#af4"><personName><givenNames>Manfred</givenNames><familyName>Zabel</familyName></personName></creator></creators><affiliationGroup><affiliation xml:id="af1" countryCode="DZ" type="organization"><unparsedAffiliation>Departement de Chimie, Faculté des Sciences Exactes, Université Mentouri‐Constantine, 25000 Constantine, Algeria</unparsedAffiliation></affiliation><affiliation xml:id="af2" countryCode="FR" type="organization"><unparsedAffiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</unparsedAffiliation></affiliation><affiliation xml:id="af3" countryCode="FR" type="organization"><unparsedAffiliation>Institut de Chimie Moléculaire de l'Université de Bourgogne ICMUB‐UMR CNRS 5260, Faculté des Sciences Mirande, Université de Bourgogne, 21100 Dijon, France</unparsedAffiliation></affiliation><affiliation xml:id="af4" countryCode="DE" type="organization"><unparsedAffiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">Cobalt</keyword><keyword xml:id="kwd2">Tellurium</keyword><keyword xml:id="kwd3">Cluster</keyword><keyword xml:id="kwd4">Electrochemistry</keyword><keyword xml:id="kwd5">Electronic structure</keyword></keywordGroup><fundingInfo><fundingAgency>Deutsche Forschungsgemeinschaft (DFG)</fundingAgency></fundingInfo><fundingInfo><fundingAgency>French‐Algerian Comité Mixte d'Evaluation et de Perspective </fundingAgency><fundingNumber>CMEP/02 MD U552</fundingNumber></fundingInfo><fundingInfo><fundingAgency>Algerian Government</fundingAgency></fundingInfo><fundingInfo><fundingAgency>Institut Universitaire de France (IUF)</fundingAgency></fundingInfo><supportingInformation><p>Supporting information for this article is available on the WWW under <url href="http://www.wiley-vch.de/contents/jc_2005/2008/i200701350_s.pdf">http://www.wiley‐vch.de/contents/jc_2005/2008/i200701350_s.pdf</url> or from the author.</p></supportingInformation><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>Extended investigations of the reaction sequence [Cp′<sub>2</sub>Nb(Te<sub>2</sub>)H]/CH<sub>3</sub>Li/[Co<sub>2</sub>(CO)<sub>8</sub>] (Cp′ = <i>t</i>BuC<sub>5</sub>H<sub>4</sub>) led to the identification of Li<i><sub>n</sub></i>[<b>3</b>] {<b>3</b> = [Co<sub>9</sub>Te<sub>6</sub>(CO)<sub>8</sub>]; <i>n</i> = 1, 2} salts through their transformation with [PPN]Cl into [PPN]<i><sub>n</sub></i>[<b>3</b>] (PPN = Ph<sub>3</sub>PNPPh<sub>3</sub>). These compounds form in the solid state columnar ([PPN][<b>3</b>]) or undulated 2D ([PPN]<sub>2</sub>[<b>3</b>]) supramolecular networks. Electrochemical studies of [Cp*<sub>2</sub>Nb(CO)<sub>2</sub>][<b>3</b>] (Cp* = C<sub>5</sub>Me<sub>5</sub>) or [Na(THF)<sub>6</sub>][<b>3</b>] revealed the presence of the redox couples [<b>3</b>]<sup>–</sup>/[<b>3</b>]<sup>2–</sup>/[<b>3</b>]<sup>3–</sup>/[<b>3</b>]<sup>4–</sup>/[<b>3</b>]<sup>5–</sup> regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [<b>3</b>]<sup>–</sup> containing salts form with PPh<sub>3</sub>AuCl or dppe decomposition products like [(PPh<sub>3</sub>)<sub>2</sub>Au][CoCl<sub>3</sub>PPh<sub>3</sub>] or [Co(CO)<sub>2</sub>dppe]<sub>2</sub>(μ‐Te). A neutral cluster comprising the Co@Co<sub>8</sub>(μ<sub>4</sub>‐Te)<sub>6</sub> core formed in the reaction of [Cp*<sub>2</sub>Nb(CO)<sub>2</sub>][Co<sub>11</sub>Te<sub>7</sub>(CO)<sub>10</sub>] with PPh<sub>3</sub>AuCl, which gave [Co<sub>9</sub>Te<sub>6</sub>(CO)<sub>4</sub>(PPh<sub>3</sub>)<sub>4</sub>] (<b>4</b>) after oxidative cluster degradation and CO substitution. <b>4</b> was characterized by X‐ray crystallography. DFT calculations carried out on all members of the [<b>3</b>]<sup><i>n</i></sup> (<i>n</i> = +1 to –5) family and on related species indicate that there is no significant Jahn–Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][<b>3</b>] show that the ground state of [<b>3</b>]<sup>–</sup> is a spin triplet with spins interacting antiferromagnetically in a 1D space.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</p></abstract><abstract type="graphical" xml:lang="en"><p>A series of cobalt‐centered hexacapped clusters containg the Co<sub>9</sub>(μ<sub>4</sub>‐Te)<sub>6</sub>L<sub>8</sub> core is described in which the metal electron count (MVE) ranges from 120 to 126 MVE. Structural, electrochemical (including the [Cp*<sub>2</sub>Nb(CO)<sub>2</sub>]<sup>+</sup> cation) and theoretical investigations prove the remarkable electron‐sponge behavior of this class of compounds. <blockFixed type="graphic"><mediaResourceGroup><mediaResource alt="image" eRights="yes" copyright="WILEY-VCH" href="urn:x-wiley:14341948:media:EJIC200701350:fig000"></mediaResource><mediaResource alt="thumbnail image" rendition="webLoRes" mimeType="image/gif" href=""></mediaResource><mediaResource alt="original image" rendition="webOriginal" mimeType="image/jpeg" href=""></mediaResource><mediaResource alt="magnified image" rendition="webHiRes" mimeType="image/jpeg" href=""></mediaResource></mediaResourceGroup></blockFixed></p></abstract></abstractGroup></contentMeta></header></component></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters</title></titleInfo><titleInfo type="abbreviated" lang="en"><title>Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>Electron‐Sponge Behavior, Reactivity and Electronic Structures of Cobalt‐Centered Cubic Co9Te6(CO)8 Clusters</title></titleInfo><name type="personal"><namePart type="given">Mustapha</namePart><namePart type="family">Bencharif</namePart><affiliation>Departement de Chimie, Faculté des Sciences Exactes, Université Mentouri‐Constantine, 25000 Constantine, Algeria</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Olivier</namePart><namePart type="family">Cador</namePart><affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Hélène</namePart><namePart type="family">Cattey</namePart><affiliation>Institut de Chimie Moléculaire de l'Université de Bourgogne ICMUB‐UMR CNRS 5260, Faculté des Sciences Mirande, Université de Bourgogne, 21100 Dijon, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Alexander</namePart><namePart type="family">Ebner</namePart><affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Jean‐François</namePart><namePart type="family">Halet</namePart><affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Samia</namePart><namePart type="family">Kahlal</namePart><affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Walter</namePart><namePart type="family">Meier</namePart><affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Yves</namePart><namePart type="family">Mugnier</namePart><affiliation>Institut de Chimie Moléculaire de l'Université de Bourgogne ICMUB‐UMR CNRS 5260, Faculté des Sciences Mirande, Université de Bourgogne, 21100 Dijon, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Jean‐Yves</namePart><namePart type="family">Saillard</namePart><affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Patrick</namePart><namePart type="family">Schwarz</namePart><affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Fatima Zohra</namePart><namePart type="family">Trodi</namePart><affiliation>Departement de Chimie, Faculté des Sciences Exactes, Université Mentouri‐Constantine, 25000 Constantine, Algeria</affiliation><affiliation>Sciences Chimiques de Rennes (UMR 6226), Université de Rennes 1, 35042 Rennes Cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Joachim</namePart><namePart type="family">Wachter</namePart><affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</affiliation><affiliation>E-mail: joachim.wachter@chemie.uni‐regensburg.de</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Manfred</namePart><namePart type="family">Zabel</namePart><affiliation>Institut für Anorganische Chemie, Universität Regensburg, 93040 Regensburg, Germany</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="book-reviews" displayLabel="bookReview"></genre><originInfo><publisher>WILEY‐VCH Verlag</publisher><place><placeTerm type="text">Weinheim</placeTerm></place><dateIssued encoding="w3cdtf">2008-04</dateIssued><dateCaptured encoding="w3cdtf">2007-12-18</dateCaptured><copyrightDate encoding="w3cdtf">2008</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">11</extent><extent unit="tables">3</extent><extent unit="references">25</extent></physicalDescription><abstract>Extended investigations of the reaction sequence [Cp′2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp′ = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3]–/[3]2–/[3]3–/[3]4–/[3]5– regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3]– containing salts form with PPh3AuCl or dppe decomposition products like [(PPh3)2Au][CoCl3PPh3] or [Co(CO)2dppe]2(μ‐Te). A neutral cluster comprising the Co@Co8(μ4‐Te)6 core formed in the reaction of [Cp*2Nb(CO)2][Co11Te7(CO)10] with PPh3AuCl, which gave [Co9Te6(CO)4(PPh3)4] (4) after oxidative cluster degradation and CO substitution. 4 was characterized by X‐ray crystallography. DFT calculations carried out on all members of the [3]n (n = +1 to –5) family and on related species indicate that there is no significant Jahn–Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][3] show that the ground state of [3]– is a spin triplet with spins interacting antiferromagnetically in a 1D space.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</abstract><abstract type="graphical" lang="en">A series of cobalt‐centered hexacapped clusters containg the Co9(μ4‐Te)6L8 core is described in which the metal electron count (MVE) ranges from 120 to 126 MVE. Structural, electrochemical (including the [Cp*2Nb(CO)2]+ cation) and theoretical investigations prove the remarkable electron‐sponge behavior of this class of compounds.</abstract><note type="funding">Deutsche Forschungsgemeinschaft (DFG)</note><note type="funding">French‐Algerian Comité Mixte d'Evaluation et de Perspective - No. CMEP/02 MD U552; </note><note type="funding">Algerian Government</note><note type="funding">Institut Universitaire de France (IUF)</note><subject lang="en"><genre>keywords</genre><topic>Cobalt</topic><topic>Tellurium</topic><topic>Cluster</topic><topic>Electrochemistry</topic><topic>Electronic structure</topic></subject><relatedItem type="host"><titleInfo><title>European Journal of Inorganic Chemistry</title></titleInfo><titleInfo type="abbreviated"><title>Eur. J. Inorg. Chem.</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_2005/2008/i200701350_s.pdf or from the author.</note><subject><genre>article-category</genre><topic>Full Paper</topic></subject><identifier type="ISSN">1434-1948</identifier><identifier type="eISSN">1099-0682</identifier><identifier type="DOI">10.1002/(ISSN)1099-0682c</identifier><identifier type="PublisherID">EJIC</identifier><part><date>2008</date><detail type="volume"><caption>vol.</caption><number>2008</number></detail><detail type="issue"><caption>no.</caption><number>12</number></detail><extent unit="pages"><start>1959</start><end>1968</end><total>10</total></extent></part></relatedItem><identifier type="istex">A3880727306C37B2B0BB6632BAD51CE31A841019</identifier><identifier type="DOI">10.1002/ejic.200701350</identifier><identifier type="ArticleID">EJIC200701350</identifier><accessCondition type="use and reproduction" contentType="copyright">Copyright © 2008 WILEY‐VCH Verlag GmbH & Co. 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