The Stereospecific Ligand Exchange at a Pseudo‐Benzylic T‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η6‐Arene)tricarbonylchromium Complexes
Identifieur interne : 001644 ( Istex/Corpus ); précédent : 001643; suivant : 001645The Stereospecific Ligand Exchange at a Pseudo‐Benzylic T‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η6‐Arene)tricarbonylchromium Complexes
Auteurs : Jean-Pierre Djukic ; Cédric Boulho ; Dusan Sredojevic ; Carla Scheeren ; Snezana Zaric ; Louis Ricard ; Michel PfefferSource :
- Chemistry – A European Journal [ 0947-6539 ] ; 2009-10-19.
English descriptors
Abstract
The stereospecificity of ligand exchange at the IrIII centre of a cycloiridium arenetricarbonylchromium complex has been established experimentally by various analytical methods as well as by X‐ray diffraction structural analysis and computational investigations. Two new cases of phenyl and methyl iridium(III) complexes have been prepared by reaction of (${S{{{\ast}\hfill \atop {\rm p}\hfill}}}$,${R{{{\ast}\hfill \atop {\rm Ir}\hfill}}}$)‐chlorido{2‐[(tricarbonyl)(η6‐phenylene‐κC1′)chromium(0)]pyridine‐κN}(pentamethylcyclopentadienyl)iridium(III) with PhMgBr and MeMgBr. The determining influence of electrostatic repulsion has been established by means of density functional theory at the Becke–Perdew/TZP(ZORA) level by using, among other means, energy partitioning analysis. It is also shown that the Cr(CO)3 fragment is likely to ease the ionic cleavage of the IrCl bond in chlorido cycloiridium tricarbonylchromium complexes in a way similar to that already established for the solvolysis of benzyl halide complexes, that is, through a direct interaction of the Cr0 centre with the cationic IrIII centre.
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DOI: 10.1002/chem.200901344
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Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</mods:affiliation></affiliation></author><author><name sortKey="Sredojevic, Dusan" sort="Sredojevic, Dusan" uniqKey="Sredojevic D" first="Dusan" last="Sredojevic">Dusan Sredojevic</name><affiliation><mods:affiliation>Department of Chemistry, University of Belgrade, Studentky Trg , 11000 Belgrade (Serbia)</mods:affiliation></affiliation></author><author><name sortKey="Scheeren, Carla" sort="Scheeren, Carla" uniqKey="Scheeren C" first="Carla" last="Scheeren">Carla Scheeren</name><affiliation><mods:affiliation>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</mods:affiliation></affiliation></author><author><name sortKey="Zaric, Snezana" sort="Zaric, Snezana" uniqKey="Zaric S" first="Snezana" last="Zaric">Snezana Zaric</name><affiliation><mods:affiliation>Department of Chemistry, University of 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390‐24‐50‐01</mods:affiliation></affiliation></author><author><name sortKey="Zaric, Snezana" sort="Zaric, Snezana" uniqKey="Zaric S" first="Snezana" last="Zaric">Snezana Zaric</name><affiliation><mods:affiliation>Department of Chemistry, University of Belgrade, Studentky Trg , 11000 Belgrade (Serbia)</mods:affiliation></affiliation></author><author><name sortKey="Ricard, Louis" sort="Ricard, Louis" uniqKey="Ricard L" first="Louis" last="Ricard">Louis Ricard</name><affiliation><mods:affiliation>Laboratoire “Hétéroéléments et Coordination”, CNRS, École Polytechnique, Route de Saclay, 91128 Palaiseau Cedex (France)</mods:affiliation></affiliation></author><author><name sortKey="Pfeffer, Michel" sort="Pfeffer, Michel" uniqKey="Pfeffer M" first="Michel" last="Pfeffer">Michel Pfeffer</name><affiliation><mods:affiliation>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 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Two new cases of phenyl and methyl iridium(III) complexes have been prepared by reaction of (${S{{{\ast}\hfill \atop {\rm p}\hfill}}}$,${R{{{\ast}\hfill \atop {\rm Ir}\hfill}}}$)‐chlorido{2‐[(tricarbonyl)(η6‐phenylene‐κC1′)chromium(0)]pyridine‐κN}(pentamethylcyclopentadienyl)iridium(III) with PhMgBr and MeMgBr. The determining influence of electrostatic repulsion has been established by means of density functional theory at the Becke–Perdew/TZP(ZORA) level by using, among other means, energy partitioning analysis. It is also shown that the Cr(CO)3 fragment is likely to ease the ionic cleavage of the IrCl bond in chlorido cycloiridium tricarbonylchromium complexes in a way similar to that already established for the solvolysis of benzyl halide complexes, that is, through a direct interaction of the Cr0 centre with the cationic IrIII centre.</div></front></TEI><istex><corpusName>wiley</corpusName><author><json:item><name>Jean‐Pierre Djukic Dr.</name><affiliations><json:string>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</json:string><json:string>E-mail: djukic@unistra.fr</json:string></affiliations></json:item><json:item><name>Cédric Boulho Dr.</name><affiliations><json:string>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</json:string></affiliations></json:item><json:item><name>Dusan Sredojevic</name><affiliations><json:string>Department of Chemistry, University of Belgrade, Studentky Trg , 11000 Belgrade (Serbia)</json:string></affiliations></json:item><json:item><name>Carla Scheeren Dr.</name><affiliations><json:string>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</json:string></affiliations></json:item><json:item><name>Snezana Zaric Prof. Dr.</name><affiliations><json:string>Department of Chemistry, University of Belgrade, Studentky Trg , 11000 Belgrade (Serbia)</json:string></affiliations></json:item><json:item><name>Louis Ricard Dr.</name><affiliations><json:string>Laboratoire “Hétéroéléments et Coordination”, CNRS, École Polytechnique, Route de Saclay, 91128 Palaiseau Cedex (France)</json:string></affiliations></json:item><json:item><name>Michel Pfeffer Dr.</name><affiliations><json:string>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>chirality</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>metallacycles</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>organometallic compounds</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>stereoisomerization</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>stereoselectivity</value></json:item></subject><articleId><json:string>CHEM200901344</json:string></articleId><language><json:string>eng</json:string></language><originalGenre><json:string>article</json:string></originalGenre><abstract>The stereospecificity of ligand exchange at the IrIII centre of a cycloiridium arenetricarbonylchromium complex has been established experimentally by various analytical methods as well as by X‐ray diffraction structural analysis and computational investigations. Two new cases of phenyl and methyl iridium(III) complexes have been prepared by reaction of (${S{{{\ast}\hfill \atop {\rm p}\hfill}}}$,${R{{{\ast}\hfill \atop {\rm Ir}\hfill}}}$)‐chlorido{2‐[(tricarbonyl)(η6‐phenylene‐κC1′)chromium(0)]pyridine‐κN}(pentamethylcyclopentadienyl)iridium(III) with PhMgBr and MeMgBr. The determining influence of electrostatic repulsion has been established by means of density functional theory at the Becke–Perdew/TZP(ZORA) level by using, among other means, energy partitioning analysis. It is also shown that the Cr(CO)3 fragment is likely to ease the ionic cleavage of the IrCl bond in chlorido cycloiridium tricarbonylchromium complexes in a way similar to that already established for the solvolysis of benzyl halide complexes, that is, through a direct interaction of the Cr0 centre with the cationic IrIII centre.</abstract><qualityIndicators><score>6.68</score><pdfVersion>1.3</pdfVersion><pdfPageSize>595.276 x 841.89 pts (A4)</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>5</keywordCount><abstractCharCount>1116</abstractCharCount><pdfWordCount>9391</pdfWordCount><pdfCharCount>55362</pdfCharCount><pdfPageCount>13</pdfPageCount><abstractWordCount>140</abstractWordCount></qualityIndicators><title>The Stereospecific Ligand Exchange at a Pseudo‐Benzylic T‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η6‐Arene)tricarbonylchromium Complexes</title><genre><json:string>article</json:string></genre><host><volume>15</volume><publisherId><json:string>CHEM</json:string></publisherId><pages><total>13</total><last>10842</last><first>10830</first></pages><issn><json:string>0947-6539</json:string></issn><issue>41</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>2009</publicationDate><copyrightDate>2009</copyrightDate><doi><json:string>10.1002/chem.200901344</json:string></doi><id>A56A48079BF83037164E6A17AED487CAA805B9C1</id><score>0.22328019</score><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/A56A48079BF83037164E6A17AED487CAA805B9C1/fulltext/pdf</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/A56A48079BF83037164E6A17AED487CAA805B9C1/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/A56A48079BF83037164E6A17AED487CAA805B9C1/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">The Stereospecific Ligand Exchange at a Pseudo‐Benzylic T‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η6‐Arene)tricarbonylchromium Complexes</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><availability><p>Copyright © 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</p></availability><date>2009</date></publicationStmt><notesStmt><note>National Research Agency - No. ANR‐06‐JCJC 0086‐01;</note><note>Centre National de la Recherche Scientifique</note><note>Ministry of Research of Serbia - No. CNRS‐MSCI 20510;</note><note>Brazilian–French CAPES‐COFECUB - No. 502/05;</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a" type="main" xml:lang="en">The Stereospecific Ligand Exchange at a Pseudo‐Benzylic T‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η6‐Arene)tricarbonylchromium Complexes</title><author xml:id="author-1"><persName><forename type="first">Jean‐Pierre</forename><surname>Djukic</surname></persName><roleName type="degree">Dr.</roleName><email>djukic@unistra.fr</email><affiliation>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</affiliation></author><author xml:id="author-2"><persName><forename type="first">Cédric</forename><surname>Boulho</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</affiliation></author><author xml:id="author-3"><persName><forename type="first">Dusan</forename><surname>Sredojevic</surname></persName><affiliation>Department of Chemistry, University of Belgrade, Studentky Trg , 11000 Belgrade (Serbia)</affiliation></author><author xml:id="author-4"><persName><forename type="first">Carla</forename><surname>Scheeren</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</affiliation></author><author xml:id="author-5"><persName><forename type="first">Snezana</forename><surname>Zaric</surname></persName><roleName type="degree">Prof. Dr.</roleName><affiliation>Department of Chemistry, University of Belgrade, Studentky Trg , 11000 Belgrade (Serbia)</affiliation></author><author xml:id="author-6"><persName><forename type="first">Louis</forename><surname>Ricard</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Laboratoire “Hétéroéléments et Coordination”, CNRS, École Polytechnique, Route de Saclay, 91128 Palaiseau Cedex (France)</affiliation></author><author xml:id="author-7"><persName><forename type="first">Michel</forename><surname>Pfeffer</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</affiliation></author></analytic><monogr><title level="j">Chemistry – A European Journal</title><title level="j" type="abbrev">Chem. Eur. J.</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="2009-10-19"></date><biblScope unit="volume">15</biblScope><biblScope unit="issue">41</biblScope><biblScope unit="page" from="10830">10830</biblScope><biblScope unit="page" to="10842">10842</biblScope></imprint></monogr><idno type="istex">A56A48079BF83037164E6A17AED487CAA805B9C1</idno><idno type="DOI">10.1002/chem.200901344</idno><idno type="ArticleID">CHEM200901344</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2009</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The stereospecificity of ligand exchange at the IrIII centre of a cycloiridium arenetricarbonylchromium complex has been established experimentally by various analytical methods as well as by X‐ray diffraction structural analysis and computational investigations. Two new cases of phenyl and methyl iridium(III) complexes have been prepared by reaction of (${S{{{\ast}\hfill \atop {\rm p}\hfill}}}$,${R{{{\ast}\hfill \atop {\rm Ir}\hfill}}}$)‐chlorido{2‐[(tricarbonyl)(η6‐phenylene‐κC1′)chromium(0)]pyridine‐κN}(pentamethylcyclopentadienyl)iridium(III) with PhMgBr and MeMgBr. The determining influence of electrostatic repulsion has been established by means of density functional theory at the Becke–Perdew/TZP(ZORA) level by using, among other means, energy partitioning analysis. It is also shown that the Cr(CO)3 fragment is likely to ease the ionic cleavage of the IrCl bond in chlorido cycloiridium tricarbonylchromium complexes in a way similar to that already established for the solvolysis of benzyl halide complexes, that is, through a direct interaction of the Cr0 centre with the cationic IrIII centre.</p></abstract><abstract><p>A neighbouring metal effect: Experimental and theoretical investigations indicate that the thermodynamically controlled nucleophilic ligand exchange at the tetrahedral iridium centre of a cycloiridium (η6‐arene)tricarbonylchromium complex is mostly ruled by the electrostatic repulsion operated by the Cr(CO)3 moiety (see graphic; NBO=natural bond orbital).</p></abstract><textClass xml:lang="en"><keywords scheme="keyword"><list><head>keywords</head><item><term>chirality</term></item><item><term>metallacycles</term></item><item><term>organometallic compounds</term></item><item><term>stereoisomerization</term></item><item><term>stereoselectivity</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="2009-05-19">Received</change><change when="2009-10-19">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/A56A48079BF83037164E6A17AED487CAA805B9C1/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" sort="CHEMISTRY - A EUROPEAN JOURNAL">Chemistry – A European Journal</title><title type="short">Chem. Eur. J.</title></titleGroup></publicationMeta><publicationMeta level="part" position="410"><doi origin="wiley" registered="yes">10.1002/chem.v15:41</doi><numberingGroup><numbering type="journalVolume" number="15">15</numbering><numbering type="journalIssue">41</numbering></numberingGroup><coverDate startDate="2009-10-19">October 19, 2009</coverDate></publicationMeta><publicationMeta level="unit" type="article" position="24" status="forIssue"><doi origin="wiley" registered="yes">10.1002/chem.200901344</doi><idGroup><id type="unit" value="CHEM200901344"></id></idGroup><countGroup><count type="pageTotal" number="13"></count></countGroup><titleGroup><title type="articleCategory">Full Paper</title><title type="tocHeading1">Full Papers</title><title type="tocHeading2">Metallacycles</title></titleGroup><copyright ownership="publisher">Copyright © 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</copyright><eventGroup><event type="manuscriptReceived" date="2009-05-19"></event><event type="firstOnline" date="2009-08-28"></event><event type="publishedOnlineFinalForm" date="2009-10-13"></event><event type="publishedOnlineAcceptedOrEarlyUnpaginated" date="2009-08-28"></event><event type="xmlConverted" agent="Converter:JWSART34_TO_WML3G version:3.2.3 mode:FullText mathml2tex" date="2013-08-07"></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">10830</numbering><numbering type="pageLast">10842</numbering></numberingGroup><objectNameGroup><objectName elementName="figure">Scheme</objectName></objectNameGroup><linkGroup><link type="toTypesetVersion" href="file:CHEM.CHEM200901344.pdf"></link></linkGroup></publicationMeta><contentMeta><countGroup><count type="figureTotal" number="17"></count><count type="tableTotal" number="4"></count><count type="referenceTotal" number="93"></count></countGroup><titleGroup><title type="main" xml:lang="en">The Stereospecific Ligand Exchange at a Pseudo‐Benzylic <i>T</i>‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η<sup>6</sup>‐Arene)tricarbonylchromium Complexes</title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Jean‐Pierre</givenNames><familyName>Djukic</familyName><degrees>Dr.</degrees></personName><contactDetails><email>djukic@unistra.fr</email></contactDetails></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Cédric</givenNames><familyName>Boulho</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au3" creatorRole="author" affiliationRef="#ab"><personName><givenNames>Dusan</givenNames><familyName>Sredojevic</familyName></personName></creator><creator xml:id="au4" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Carla</givenNames><familyName>Scheeren</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au5" creatorRole="author" affiliationRef="#ab"><personName><givenNames>Snezana</givenNames><familyName>Zaric</familyName><degrees>Prof. Dr.</degrees></personName></creator><creator xml:id="au6" creatorRole="author" affiliationRef="#ac"><personName><givenNames>Louis</givenNames><familyName>Ricard</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au7" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Michel</givenNames><familyName>Pfeffer</familyName><degrees>Dr.</degrees></personName></creator></creators><affiliationGroup><affiliation xml:id="aa" countryCode="FR" type="organization"><unparsedAffiliation>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</unparsedAffiliation></affiliation><affiliation xml:id="ab" countryCode="RS" type="organization"><unparsedAffiliation>Department of Chemistry, University of Belgrade, Studentky Trg , 11000 Belgrade (Serbia)</unparsedAffiliation></affiliation><affiliation xml:id="ac" countryCode="FR" type="organization"><unparsedAffiliation>Laboratoire “Hétéroéléments et Coordination”, CNRS, École Polytechnique, Route de Saclay, 91128 Palaiseau Cedex (France)</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">chirality</keyword><keyword xml:id="kwd2">metallacycles</keyword><keyword xml:id="kwd3">organometallic compounds</keyword><keyword xml:id="kwd4">stereoisomerization</keyword><keyword xml:id="kwd5">stereoselectivity</keyword></keywordGroup><fundingInfo><fundingAgency>National Research Agency</fundingAgency><fundingNumber>ANR‐06‐JCJC 0086‐01</fundingNumber></fundingInfo><fundingInfo><fundingAgency>Centre National de la Recherche Scientifique</fundingAgency></fundingInfo><fundingInfo><fundingAgency>Ministry of Research of Serbia</fundingAgency><fundingNumber>CNRS‐MSCI 20510</fundingNumber></fundingInfo><fundingInfo><fundingAgency>Brazilian–French CAPES‐COFECUB</fundingAgency><fundingNumber>502/05</fundingNumber></fundingInfo><supportingInformation><p>Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer‐reviewed, but not copy‐edited or typeset. They are made available as submitted by the authors. </p><supportingInfoItem><mediaResource alt="supporting information" href="urn-x:wiley:09476539:media:chem200901344:chem_200901344_sm_miscellaneous_information"></mediaResource><caption>miscellaneous_information</caption></supportingInfoItem></supportingInformation><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>The stereospecificity of ligand exchange at the Ir<sup>III</sup> centre of a cycloiridium arenetricarbonylchromium complex has been established experimentally by various analytical methods as well as by X‐ray diffraction structural analysis and computational investigations. Two new cases of phenyl and methyl iridium(III) complexes have been prepared by reaction of (<span type="tex">${S{{{\ast}\hfill \atop {\rm p}\hfill}}}$<inlineGraphic alt="equation image" location="equation/tex2gif-ueqn-1.gif" href=""></inlineGraphic></span>,<span type="tex">${R{{{\ast}\hfill \atop {\rm Ir}\hfill}}}$<inlineGraphic alt="equation image" location="equation/tex2gif-ueqn-2.gif" href=""></inlineGraphic></span>)‐chlorido{2‐[(tricarbonyl)(η<sup>6</sup>‐phenylene‐κ<i>C</i><sup>1′</sup>)chromium(0)]pyridine‐κ<i>N</i>}(pentamethylcyclopentadienyl)iridium(III) with PhMgBr and MeMgBr. The determining influence of electrostatic repulsion has been established by means of density functional theory at the Becke–Perdew/TZP(ZORA) level by using, among other means, energy partitioning analysis. It is also shown that the Cr(CO)<sub>3</sub> fragment is likely to ease the ionic cleavage of the IrCl bond in chlorido cycloiridium tricarbonylchromium complexes in a way similar to that already established for the solvolysis of benzyl halide complexes, that is, through a direct interaction of the Cr<sup>0</sup> centre with the cationic Ir<sup>III</sup> centre.</p></abstract><abstract type="graphical" xml:lang="en"><p><b>A neighbouring metal effect</b>: Experimental and theoretical investigations indicate that the thermodynamically controlled nucleophilic ligand exchange at the tetrahedral iridium centre of a cycloiridium (η<sup>6</sup>‐arene)tricarbonylchromium complex is mostly ruled by the electrostatic repulsion operated by the Cr(CO)<sub>3</sub> moiety (see graphic; NBO=natural bond orbital).<blockFixed type="graphic"><mediaResourceGroup><mediaResource alt="image" eRights="yes" copyright="WILEY-VCH" href="urn:x-wiley:09476539:media:CHEM200901344: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 Stereospecific Ligand Exchange at a Pseudo‐Benzylic T‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η6‐Arene)tricarbonylchromium Complexes</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>The Stereospecific Ligand Exchange at a Pseudo‐Benzylic T‐4 Iridium Centre in Planar‐Chiral Cycloiridium (η6‐Arene)tricarbonylchromium Complexes</title></titleInfo><name type="personal"><namePart type="given">Jean‐Pierre</namePart><namePart type="family">Djukic</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</affiliation><affiliation>E-mail: djukic@unistra.fr</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Cédric</namePart><namePart type="family">Boulho</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Dusan</namePart><namePart type="family">Sredojevic</namePart><affiliation>Department of Chemistry, University of Belgrade, Studentky Trg , 11000 Belgrade (Serbia)</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Carla</namePart><namePart type="family">Scheeren</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Snezana</namePart><namePart type="family">Zaric</namePart><namePart type="termsOfAddress">Prof. Dr.</namePart><affiliation>Department of Chemistry, University of Belgrade, Studentky Trg , 11000 Belgrade (Serbia)</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Louis</namePart><namePart type="family">Ricard</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire “Hétéroéléments et Coordination”, CNRS, École Polytechnique, Route de Saclay, 91128 Palaiseau Cedex (France)</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Michel</namePart><namePart type="family">Pfeffer</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire de Synthèses métallo‐induites, Institut de Chimie, CNRS, Université de Strasbourg, 4 rue Blaise Pascal, 67070 Strasbourg Cedex (France), Fax: (+33) 390‐24‐50‐01</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">2009-10-19</dateIssued><dateCaptured encoding="w3cdtf">2009-05-19</dateCaptured><copyrightDate encoding="w3cdtf">2009</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">17</extent><extent unit="tables">4</extent><extent unit="references">93</extent></physicalDescription><abstract lang="en">The stereospecificity of ligand exchange at the IrIII centre of a cycloiridium arenetricarbonylchromium complex has been established experimentally by various analytical methods as well as by X‐ray diffraction structural analysis and computational investigations. Two new cases of phenyl and methyl iridium(III) complexes have been prepared by reaction of (${S{{{\ast}\hfill \atop {\rm p}\hfill}}}$,${R{{{\ast}\hfill \atop {\rm Ir}\hfill}}}$)‐chlorido{2‐[(tricarbonyl)(η6‐phenylene‐κC1′)chromium(0)]pyridine‐κN}(pentamethylcyclopentadienyl)iridium(III) with PhMgBr and MeMgBr. The determining influence of electrostatic repulsion has been established by means of density functional theory at the Becke–Perdew/TZP(ZORA) level by using, among other means, energy partitioning analysis. It is also shown that the Cr(CO)3 fragment is likely to ease the ionic cleavage of the IrCl bond in chlorido cycloiridium tricarbonylchromium complexes in a way similar to that already established for the solvolysis of benzyl halide complexes, that is, through a direct interaction of the Cr0 centre with the cationic IrIII centre.</abstract><abstract>A neighbouring metal effect: Experimental and theoretical investigations indicate that the thermodynamically controlled nucleophilic ligand exchange at the tetrahedral iridium centre of a cycloiridium (η6‐arene)tricarbonylchromium complex is mostly ruled by the electrostatic repulsion operated by the Cr(CO)3 moiety (see graphic; NBO=natural bond orbital).</abstract><note type="funding">National Research Agency - No. ANR‐06‐JCJC 0086‐01; </note><note type="funding">Centre National de la Recherche Scientifique</note><note type="funding">Ministry of Research of Serbia - No. CNRS‐MSCI 20510; </note><note type="funding">Brazilian–French CAPES‐COFECUB - No. 502/05; </note><subject lang="en"><genre>keywords</genre><topic>chirality</topic><topic>metallacycles</topic><topic>organometallic compounds</topic><topic>stereoisomerization</topic><topic>stereoselectivity</topic></subject><relatedItem type="host"><titleInfo><title>Chemistry – A European Journal</title></titleInfo><titleInfo type="abbreviated"><title>Chem. Eur. J.</title></titleInfo><genre type="journal">journal</genre><note type="content"> Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer‐reviewed, but not copy‐edited or typeset. 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