Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds
Identifieur interne : 001631 ( Istex/Corpus ); précédent : 001630; suivant : 001632Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds
Auteurs : Michael Knorr ; Isabelle Jourdain ; Grégorio Crini ; Katja Frank ; Hermann Sachdev ; Carsten StrohmannSource :
- European Journal of Inorganic Chemistry [ 1434-1948 ] ; 2002-09.
English descriptors
- KwdEn :
- Teeft :
- Adjacent metal centers, Ambient temperature, Anisotropic refinement, Approximate dimensions, Benzyl, Bond lengths, Braunstein, Calcd, Carbonyl, Carbonyl ligand, Chem, Chemical shifts, Covalent bond, Crystal structure, Crystalline state, Crystallographic data, Cyclohexyl, Cyclohexyl isocyanide, Dalton trans, Dative, Dative bond, Diffraction study, Electron density, Electron density crystal structure determination, Equatorial carbonyl ligands, Full paper, Heterobimetallic isocyanide complexes, Hydrogen atoms, Ideal value, Independent reflections, Inorg, Intensity data, Iron center, Isocyanide, Isocyanide complexes, Isocyanide ligand, Knorr, Latter case, Ligand, Metal atoms, Metal centers, Metathesis reaction, Moderate yields, Molecular structure, Molecular structures, Organometallics, Phenyl, Phosphorus nucleus, Reactivity pattern, Scan range, Space group, Spectroscopic data, Stoichiometric amounts, Strohmann, Structural features, Structure solution, Suitable crystals, Trans, Various isocyanides, Verlag gmbh, Yellow crystals.
Abstract
When [(OC)3Fe(μ‐CO)(μ‐dppm)PtCl2] (1) is allowed to react with stoichiometric amounts of various isocyanides, cleavage of the metal−metal bond occurs, yielding the heterodinuclear isocyanide complexes [(OC)4Fe{μ‐dppm}Pt(Cl)2(CNR)] (2a: R = 2,6‐xylyl; 2b: R = o‐anisyl; 2c: R = benzyl; 2d: R = cyclohexyl; 2e: R = tosylmethyl). Reduction of 2a−2e by NaBH4 in the presence of PPh3 affords the isocyanide‐bridged complexes [(OC)3Fe(μ‐C=N−R)(μ‐dppm)Pt(PPh3)] (3a: R = 2,6‐xylyl; 3b: R = o‐anisyl; 3c: R = benzyl; 3d: R = cyclohexyl; 3e: R = tosylmethyl). Metathesis of 2a−2d with NaI rapidly results in the formation of [(OC)4Fe{μ‐dppm}PtI2(CNR)] (4a−4d), which is slowly transformed under extrusion of CO giving [(OC)2IFe{μ‐dppm}(μ‐CO)PtI(CNR)] (6a: R = 2,6‐xylyl; 6b: R = o‐anisyl; 6c: R = benzyl; 6d: R = cyclohexyl), bearing an iodine ligand at the iron center. Due to this intramolecular iodide migration from Pt to Fe, an FeI d7 fragment interacts with a PtI d9 fragment through a covalent bond. Alternatively, 6a−6d are obtained by stoichiometric treatment of [(CO)3Fe(μ‐I)(μ‐dppm)PtI] (5) with CNR. Single‐crystal X‐ray diffraction studies are performed on 2d, 2e and 3c as well as on 6d. In the solid state, the two metal centers of 2e remain in close contact (3.862 Å), whereas in the case of 2d they are separated by 6.573 Å after cleavage of the metal−metal bond by CNR. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)
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DOI: 10.1002/1099-0682(200209)2002:9<2419::AID-EJIC2419>3.0.CO;2-U
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ISTEX:D8934F7D0DB4F5512717DA5A7CF247C286FB7D74Le document en format XML
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Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Crini, Gregorio" sort="Crini, Gregorio" uniqKey="Crini G" first="Grégorio" last="Crini">Grégorio Crini</name><affiliation><mods:affiliation>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Frank, Katja" sort="Frank, Katja" uniqKey="Frank K" first="Katja" last="Frank">Katja Frank</name><affiliation><mods:affiliation>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken, Germany</mods:affiliation></affiliation></author><author><name sortKey="Sachdev, Hermann" sort="Sachdev, Hermann" uniqKey="Sachdev H" first="Hermann" last="Sachdev">Hermann Sachdev</name><affiliation><mods:affiliation>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken, Germany</mods:affiliation></affiliation></author><author><name sortKey="Strohmann, Carsten" sort="Strohmann, Carsten" uniqKey="Strohmann C" first="Carsten" last="Strohmann">Carsten Strohmann</name><affiliation><mods:affiliation>Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, 97074 Würzburg, 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="2002-09">2002-09</date><biblScope unit="volume">2002</biblScope><biblScope unit="issue">9</biblScope><biblScope unit="page" from="2419">2419</biblScope><biblScope unit="page" to="2426">2426</biblScope></imprint><idno type="ISSN">1434-1948</idno></series><idno type="istex">D8934F7D0DB4F5512717DA5A7CF247C286FB7D74</idno><idno type="DOI">10.1002/1099-0682(200209)2002:9<2419::AID-EJIC2419>3.0.CO;2-U</idno><idno type="ArticleID">EJIC2419</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">1434-1948</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Heterobimetallics</term><term>Iron</term><term>Isocyanide ligands</term><term>Metal−metal interactions</term><term>Platinum</term></keywords><keywords scheme="Teeft" xml:lang="en"><term>Adjacent metal centers</term><term>Ambient temperature</term><term>Anisotropic refinement</term><term>Approximate dimensions</term><term>Benzyl</term><term>Bond lengths</term><term>Braunstein</term><term>Calcd</term><term>Carbonyl</term><term>Carbonyl ligand</term><term>Chem</term><term>Chemical shifts</term><term>Covalent bond</term><term>Crystal structure</term><term>Crystalline state</term><term>Crystallographic data</term><term>Cyclohexyl</term><term>Cyclohexyl isocyanide</term><term>Dalton trans</term><term>Dative</term><term>Dative bond</term><term>Diffraction study</term><term>Electron density</term><term>Electron density crystal structure determination</term><term>Equatorial carbonyl ligands</term><term>Full paper</term><term>Heterobimetallic isocyanide complexes</term><term>Hydrogen atoms</term><term>Ideal value</term><term>Independent reflections</term><term>Inorg</term><term>Intensity data</term><term>Iron center</term><term>Isocyanide</term><term>Isocyanide complexes</term><term>Isocyanide ligand</term><term>Knorr</term><term>Latter case</term><term>Ligand</term><term>Metal atoms</term><term>Metal centers</term><term>Metathesis reaction</term><term>Moderate yields</term><term>Molecular structure</term><term>Molecular structures</term><term>Organometallics</term><term>Phenyl</term><term>Phosphorus nucleus</term><term>Reactivity pattern</term><term>Scan range</term><term>Space group</term><term>Spectroscopic data</term><term>Stoichiometric amounts</term><term>Strohmann</term><term>Structural features</term><term>Structure solution</term><term>Suitable crystals</term><term>Trans</term><term>Various isocyanides</term><term>Verlag gmbh</term><term>Yellow crystals</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract">When [(OC)3Fe(μ‐CO)(μ‐dppm)PtCl2] (1) is allowed to react with stoichiometric amounts of various isocyanides, cleavage of the metal−metal bond occurs, yielding the heterodinuclear isocyanide complexes [(OC)4Fe{μ‐dppm}Pt(Cl)2(CNR)] (2a: R = 2,6‐xylyl; 2b: R = o‐anisyl; 2c: R = benzyl; 2d: R = cyclohexyl; 2e: R = tosylmethyl). Reduction of 2a−2e by NaBH4 in the presence of PPh3 affords the isocyanide‐bridged complexes [(OC)3Fe(μ‐C=N−R)(μ‐dppm)Pt(PPh3)] (3a: R = 2,6‐xylyl; 3b: R = o‐anisyl; 3c: R = benzyl; 3d: R = cyclohexyl; 3e: R = tosylmethyl). Metathesis of 2a−2d with NaI rapidly results in the formation of [(OC)4Fe{μ‐dppm}PtI2(CNR)] (4a−4d), which is slowly transformed under extrusion of CO giving [(OC)2IFe{μ‐dppm}(μ‐CO)PtI(CNR)] (6a: R = 2,6‐xylyl; 6b: R = o‐anisyl; 6c: R = benzyl; 6d: R = cyclohexyl), bearing an iodine ligand at the iron center. Due to this intramolecular iodide migration from Pt to Fe, an FeI d7 fragment interacts with a PtI d9 fragment through a covalent bond. Alternatively, 6a−6d are obtained by stoichiometric treatment of [(CO)3Fe(μ‐I)(μ‐dppm)PtI] (5) with CNR. Single‐crystal X‐ray diffraction studies are performed on 2d, 2e and 3c as well as on 6d. In the solid state, the two metal centers of 2e remain in close contact (3.862 Å), whereas in the case of 2d they are separated by 6.573 Å after cleavage of the metal−metal bond by CNR. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)</div></front></TEI><istex><corpusName>wiley</corpusName><keywords><teeft><json:string>chem</json:string><json:string>isocyanide</json:string><json:string>ligand</json:string><json:string>calcd</json:string><json:string>phenyl</json:string><json:string>inorg</json:string><json:string>knorr</json:string><json:string>bond lengths</json:string><json:string>strohmann</json:string><json:string>organometallics</json:string><json:string>trans</json:string><json:string>benzyl</json:string><json:string>dalton trans</json:string><json:string>dative</json:string><json:string>braunstein</json:string><json:string>cyclohexyl</json:string><json:string>crystal structure</json:string><json:string>carbonyl ligand</json:string><json:string>isocyanide ligand</json:string><json:string>spectroscopic data</json:string><json:string>carbonyl</json:string><json:string>full paper</json:string><json:string>structure solution</json:string><json:string>dative bond</json:string><json:string>independent reflections</json:string><json:string>space group</json:string><json:string>hydrogen atoms</json:string><json:string>anisotropic refinement</json:string><json:string>intensity data</json:string><json:string>crystallographic data</json:string><json:string>metal centers</json:string><json:string>stoichiometric amounts</json:string><json:string>chemical shifts</json:string><json:string>crystalline state</json:string><json:string>scan range</json:string><json:string>approximate dimensions</json:string><json:string>heterobimetallic isocyanide complexes</json:string><json:string>molecular structure</json:string><json:string>electron density crystal structure determination</json:string><json:string>ambient temperature</json:string><json:string>iron center</json:string><json:string>metal atoms</json:string><json:string>suitable crystals</json:string><json:string>phosphorus nucleus</json:string><json:string>adjacent metal centers</json:string><json:string>various isocyanides</json:string><json:string>verlag gmbh</json:string><json:string>ideal value</json:string><json:string>molecular structures</json:string><json:string>yellow crystals</json:string><json:string>diffraction study</json:string><json:string>covalent bond</json:string><json:string>cyclohexyl isocyanide</json:string><json:string>electron density</json:string><json:string>latter case</json:string><json:string>isocyanide complexes</json:string><json:string>structural features</json:string><json:string>reactivity pattern</json:string><json:string>moderate yields</json:string><json:string>metathesis reaction</json:string><json:string>equatorial carbonyl ligands</json:string></teeft></keywords><author><json:item><name>Michael Knorr</name><affiliations><json:string>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</json:string><json:string>E-mail: michael.knorr@univ‐fcomte.fr</json:string></affiliations></json:item><json:item><name>Isabelle Jourdain</name><affiliations><json:string>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</json:string></affiliations></json:item><json:item><name>Grégorio Crini</name><affiliations><json:string>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</json:string></affiliations></json:item><json:item><name>Katja Frank</name><affiliations><json:string>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken, Germany</json:string></affiliations></json:item><json:item><name>Hermann Sachdev</name><affiliations><json:string>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken, Germany</json:string></affiliations></json:item><json:item><name>Carsten Strohmann</name><affiliations><json:string>Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, 97074 Würzburg, Germany</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>Heterobimetallics</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Isocyanide ligands</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Metal−metal interactions</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Iron</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Platinum</value></json:item></subject><articleId><json:string>EJIC2419</json:string></articleId><language><json:string>eng</json:string></language><originalGenre><json:string>article</json:string></originalGenre><abstract>When [(OC)3Fe(μ‐CO)(μ‐dppm)PtCl2] (1) is allowed to react with stoichiometric amounts of various isocyanides, cleavage of the metal−metal bond occurs, yielding the heterodinuclear isocyanide complexes [(OC)4Fe{μ‐dppm}Pt(Cl)2(CNR)] (2a: R = 2,6‐xylyl; 2b: R = o‐anisyl; 2c: R = benzyl; 2d: R = cyclohexyl; 2e: R = tosylmethyl). Reduction of 2a−2e by NaBH4 in the presence of PPh3 affords the isocyanide‐bridged complexes [(OC)3Fe(μ‐C=N−R)(μ‐dppm)Pt(PPh3)] (3a: R = 2,6‐xylyl; 3b: R = o‐anisyl; 3c: R = benzyl; 3d: R = cyclohexyl; 3e: R = tosylmethyl). Metathesis of 2a−2d with NaI rapidly results in the formation of [(OC)4Fe{μ‐dppm}PtI2(CNR)] (4a−4d), which is slowly transformed under extrusion of CO giving [(OC)2IFe{μ‐dppm}(μ‐CO)PtI(CNR)] (6a: R = 2,6‐xylyl; 6b: R = o‐anisyl; 6c: R = benzyl; 6d: R = cyclohexyl), bearing an iodine ligand at the iron center. Due to this intramolecular iodide migration from Pt to Fe, an FeI d7 fragment interacts with a PtI d9 fragment through a covalent bond. Alternatively, 6a−6d are obtained by stoichiometric treatment of [(CO)3Fe(μ‐I)(μ‐dppm)PtI] (5) with CNR. Single‐crystal X‐ray diffraction studies are performed on 2d, 2e and 3c as well as on 6d. In the solid state, the two metal centers of 2e remain in close contact (3.862 Å), whereas in the case of 2d they are separated by 6.573 Å after cleavage of the metal−metal bond by CNR. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)</abstract><qualityIndicators><score>7.676</score><pdfVersion>1.3</pdfVersion><pdfPageSize>595 x 794 pts</pdfPageSize><refBibsNative>true</refBibsNative><abstractCharCount>1435</abstractCharCount><pdfWordCount>5623</pdfWordCount><pdfCharCount>35013</pdfCharCount><pdfPageCount>8</pdfPageCount><abstractWordCount>223</abstractWordCount></qualityIndicators><title>Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds</title><genre><json:string>article</json:string></genre><host><title>European Journal of Inorganic Chemistry</title><language><json:string>unknown</json:string></language><doi><json:string>10.1002/(ISSN)1099-0682c</json:string></doi><issn><json:string>1434-1948</json:string></issn><eissn><json:string>1099-0682</json:string></eissn><publisherId><json:string>EJIC</json:string></publisherId><volume>2002</volume><issue>9</issue><pages><first>2419</first><last>2426</last><total>8</total></pages><genre><json:string>journal</json:string></genre><subject><json:item><value>Full Paper</value></json:item></subject></host><categories><wos><json:string>science</json:string><json:string>chemistry, inorganic & nuclear</json:string></wos><scienceMetrix><json:string>natural sciences</json:string><json:string>chemistry</json:string><json:string>inorganic & nuclear chemistry</json:string></scienceMetrix></categories><publicationDate>2002</publicationDate><copyrightDate>2002</copyrightDate><doi><json:string>10.1002/1099-0682(200209)2002:9>2419::AID-EJIC2419>3.0.CO;2-U</json:string></doi><id>D8934F7D0DB4F5512717DA5A7CF247C286FB7D74</id><score>1</score><fulltext><json:item><extension>pdf</extension><original>true</original><mimetype>application/pdf</mimetype><uri>https://api.istex.fr/document/D8934F7D0DB4F5512717DA5A7CF247C286FB7D74/fulltext/pdf</uri></json:item><json:item><extension>zip</extension><original>false</original><mimetype>application/zip</mimetype><uri>https://api.istex.fr/document/D8934F7D0DB4F5512717DA5A7CF247C286FB7D74/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/D8934F7D0DB4F5512717DA5A7CF247C286FB7D74/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><availability><p>© 2002 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</p></availability><date>2002</date></publicationStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a" type="main" xml:lang="en">Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds</title><author xml:id="author-1"><persName><forename type="first">Michael</forename><surname>Knorr</surname></persName><email>michael.knorr@univ‐fcomte.fr</email><affiliation>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</affiliation></author><author xml:id="author-2"><persName><forename type="first">Isabelle</forename><surname>Jourdain</surname></persName><affiliation>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</affiliation></author><author xml:id="author-3"><persName><forename type="first">Grégorio</forename><surname>Crini</surname></persName><affiliation>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</affiliation></author><author xml:id="author-4"><persName><forename type="first">Katja</forename><surname>Frank</surname></persName><affiliation>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken, Germany</affiliation></author><author xml:id="author-5"><persName><forename type="first">Hermann</forename><surname>Sachdev</surname></persName><affiliation>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken, Germany</affiliation></author><author xml:id="author-6"><persName><forename type="first">Carsten</forename><surname>Strohmann</surname></persName><affiliation>Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, 97074 Würzburg, 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="2002-09"></date><biblScope unit="volume">2002</biblScope><biblScope unit="issue">9</biblScope><biblScope unit="page" from="2419">2419</biblScope><biblScope unit="page" to="2426">2426</biblScope></imprint></monogr><idno type="istex">D8934F7D0DB4F5512717DA5A7CF247C286FB7D74</idno><idno type="DOI">10.1002/1099-0682(200209)2002:9<2419::AID-EJIC2419>3.0.CO;2-U</idno><idno type="ArticleID">EJIC2419</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2002</date></creation><langUsage><language ident="en">en</language></langUsage><abstract><p>When [(OC)3Fe(μ‐CO)(μ‐dppm)PtCl2] (1) is allowed to react with stoichiometric amounts of various isocyanides, cleavage of the metal−metal bond occurs, yielding the heterodinuclear isocyanide complexes [(OC)4Fe{μ‐dppm}Pt(Cl)2(CNR)] (2a: R = 2,6‐xylyl; 2b: R = o‐anisyl; 2c: R = benzyl; 2d: R = cyclohexyl; 2e: R = tosylmethyl). Reduction of 2a−2e by NaBH4 in the presence of PPh3 affords the isocyanide‐bridged complexes [(OC)3Fe(μ‐C=N−R)(μ‐dppm)Pt(PPh3)] (3a: R = 2,6‐xylyl; 3b: R = o‐anisyl; 3c: R = benzyl; 3d: R = cyclohexyl; 3e: R = tosylmethyl). Metathesis of 2a−2d with NaI rapidly results in the formation of [(OC)4Fe{μ‐dppm}PtI2(CNR)] (4a−4d), which is slowly transformed under extrusion of CO giving [(OC)2IFe{μ‐dppm}(μ‐CO)PtI(CNR)] (6a: R = 2,6‐xylyl; 6b: R = o‐anisyl; 6c: R = benzyl; 6d: R = cyclohexyl), bearing an iodine ligand at the iron center. Due to this intramolecular iodide migration from Pt to Fe, an FeI d7 fragment interacts with a PtI d9 fragment through a covalent bond. Alternatively, 6a−6d are obtained by stoichiometric treatment of [(CO)3Fe(μ‐I)(μ‐dppm)PtI] (5) with CNR. Single‐crystal X‐ray diffraction studies are performed on 2d, 2e and 3c as well as on 6d. In the solid state, the two metal centers of 2e remain in close contact (3.862 Å), whereas in the case of 2d they are separated by 6.573 Å after cleavage of the metal−metal bond by CNR. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)</p></abstract><textClass xml:lang="en"><keywords scheme="keyword"><list><head>keywords</head><item><term>Heterobimetallics</term></item><item><term>Isocyanide ligands</term></item><item><term>Metal−metal interactions</term></item><item><term>Iron</term></item><item><term>Platinum</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="2002-02-11">Received</change><change when="2002-09">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><extension>txt</extension><original>false</original><mimetype>text/plain</mimetype><uri>https://api.istex.fr/document/D8934F7D0DB4F5512717DA5A7CF247C286FB7D74/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="90"><doi origin="wiley" registered="yes">10.1002/1099-0682(200209)2002:9<>1.0.CO;2-J</doi><numberingGroup><numbering type="journalVolume" number="2002">2002</numbering><numbering type="journalIssue">9</numbering></numberingGroup><coverDate startDate="2002-09">September 2002</coverDate></publicationMeta><publicationMeta level="unit" type="article" position="28" status="forIssue"><doi origin="wiley" registered="yes">10.1002/1099-0682(200209)2002:9<2419::AID-EJIC2419>3.0.CO;2-U</doi><idGroup><id type="unit" value="EJIC2419"></id></idGroup><countGroup><count type="pageTotal" number="8"></count></countGroup><titleGroup><title type="articleCategory">Full Paper</title></titleGroup><copyright ownership="publisher">© 2002 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</copyright><eventGroup><event type="manuscriptReceived" date="2002-02-11"></event><event type="firstOnline" date="2002-08-05"></event><event type="publishedOnlineFinalForm" date="2002-08-05"></event><event type="xmlConverted" agent="Converter:JWSART34_TO_WML3G version:2.3.5 mode:FullText source:FullText result:FullText mathml2tex" date="2010-04-09"></event><event type="xmlConverted" agent="Converter:WILEY_ML3G_TO_WILEY_ML3GV2 version:3.8.8" date="2014-01-24"></event><event type="xmlConverted" agent="Converter:WML3G_To_WML3G version:4.1.7 mode:FullText,remove_FC" date="2014-10-16"></event></eventGroup><numberingGroup><numbering type="pageFirst">2419</numbering><numbering type="pageLast">2426</numbering></numberingGroup><objectNameGroup><objectName elementName="figure">Scheme</objectName></objectNameGroup><linkGroup><link type="toTypesetVersion" href="file:EJIC.EJIC2419.pdf"></link></linkGroup></publicationMeta><contentMeta><countGroup><count type="figureTotal" number="4"></count><count type="tableTotal" number="1"></count><count type="referenceTotal" number="39"></count></countGroup><titleGroup><title type="main" xml:lang="en">Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds</title><title type="short" xml:lang="en">Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes</title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Michael</givenNames><familyName>Knorr</familyName></personName><contactDetails><email normalForm="michael.knorr@univ-fcomte.fr">michael.knorr@univ‐fcomte.fr</email></contactDetails></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Isabelle</givenNames><familyName>Jourdain</familyName></personName></creator><creator xml:id="au3" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Grégorio</givenNames><familyName>Crini</familyName></personName></creator><creator xml:id="au4" creatorRole="author" affiliationRef="#af2"><personName><givenNames>Katja</givenNames><familyName>Frank</familyName></personName></creator><creator xml:id="au5" creatorRole="author" affiliationRef="#af2"><personName><givenNames>Hermann</givenNames><familyName>Sachdev</familyName></personName></creator><creator xml:id="au6" creatorRole="author" affiliationRef="#af3"><personName><givenNames>Carsten</givenNames><familyName>Strohmann</familyName></personName></creator></creators><affiliationGroup><affiliation xml:id="af1" countryCode="FR" type="organization"><unparsedAffiliation>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</unparsedAffiliation></affiliation><affiliation xml:id="af2" countryCode="DE" type="organization"><unparsedAffiliation>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken, Germany</unparsedAffiliation></affiliation><affiliation xml:id="af3" countryCode="DE" type="organization"><unparsedAffiliation>Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, 97074 Würzburg, Germany</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">Heterobimetallics</keyword><keyword xml:id="kwd2">Isocyanide ligands</keyword><keyword xml:id="kwd3">Metal−metal interactions</keyword><keyword xml:id="kwd4">Iron</keyword><keyword xml:id="kwd5">Platinum</keyword></keywordGroup><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>When [(OC)<sub>3</sub>Fe(μ‐CO)(μ‐dppm)PtCl<sub>2</sub>] (<b>1</b>) is allowed to react with stoichiometric amounts of various isocyanides, cleavage of the metal−metal bond occurs, yielding the heterodinuclear isocyanide complexes [(OC)<sub>4</sub>Fe{μ‐dppm}Pt(Cl)<sub>2</sub>(CNR)] (<b>2a</b>: R = 2,6‐xylyl; <b>2b</b>: R = <i>o</i>‐anisyl; <b>2c</b>: R = benzyl; <b>2d</b>: R = cyclohexyl; <b>2e</b>: R = tosylmethyl). Reduction of <b>2a</b>−<b>2e</b> by NaBH<sub>4</sub> in the presence of PPh<sub>3</sub> affords the isocyanide‐bridged complexes [(OC)<sub>3</sub>Fe(μ‐C=N−R)(μ‐dppm)Pt(PPh<sub>3</sub>)] (<b>3a</b>: R = 2,6‐xylyl; <b>3b</b>: R = <i>o</i>‐anisyl; <b>3c</b>: R = benzyl; <b>3d</b>: R = cyclohexyl; <b>3e</b>: R = tosylmethyl). Metathesis of <b>2a</b>−<b>2d</b> with NaI rapidly results in the formation of [(OC)<sub>4</sub>Fe{μ‐dppm}PtI<sub>2</sub>(CNR)] (<b>4a</b>−<b>4d</b>), which is slowly transformed under extrusion of CO giving [(OC)<sub>2</sub>IFe{μ‐dppm}(μ‐CO)PtI(CNR)] (<b>6a</b>: R = 2,6‐xylyl; <b>6b</b>: R = <i>o</i>‐anisyl; <b>6c</b>: R = benzyl; <b>6d</b>: R = cyclohexyl), bearing an iodine ligand at the iron center. Due to this intramolecular iodide migration from Pt to Fe, an Fe<sup>I</sup> d<sup>7</sup> fragment interacts with a Pt<sup>I</sup> d<sup>9</sup> fragment through a covalent bond. Alternatively, <b>6a</b>−<b>6d</b> are obtained by stoichiometric treatment of [(CO)<sub>3</sub>Fe(μ‐I)(μ‐dppm)PtI] (<b>5</b>) with CNR. Single‐crystal X‐ray diffraction studies are performed on <b>2d</b>, <b>2e</b> and <b>3c</b> as well as on<b> 6d</b>. In the solid state, the two metal centers of <b>2e</b> remain in close contact (3.862 Å), whereas in the case of <b>2d</b> they are separated by 6.573 Å after cleavage of the metal−metal bond by CNR. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)</p></abstract></abstractGroup></contentMeta></header></component></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds</title></titleInfo><titleInfo type="abbreviated" lang="en"><title>Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds</title></titleInfo><name type="personal"><namePart type="given">Michael</namePart><namePart type="family">Knorr</namePart><affiliation>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</affiliation><affiliation>E-mail: michael.knorr@univ‐fcomte.fr</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Isabelle</namePart><namePart type="family">Jourdain</namePart><affiliation>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Grégorio</namePart><namePart type="family">Crini</namePart><affiliation>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Katja</namePart><namePart type="family">Frank</namePart><affiliation>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken, Germany</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Hermann</namePart><namePart type="family">Sachdev</namePart><affiliation>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken, Germany</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Carsten</namePart><namePart type="family">Strohmann</namePart><affiliation>Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, 97074 Würzburg, Germany</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">2002-09</dateIssued><dateCaptured encoding="w3cdtf">2002-02-11</dateCaptured><copyrightDate encoding="w3cdtf">2002</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">4</extent><extent unit="tables">1</extent><extent unit="references">39</extent></physicalDescription><abstract>When [(OC)3Fe(μ‐CO)(μ‐dppm)PtCl2] (1) is allowed to react with stoichiometric amounts of various isocyanides, cleavage of the metal−metal bond occurs, yielding the heterodinuclear isocyanide complexes [(OC)4Fe{μ‐dppm}Pt(Cl)2(CNR)] (2a: R = 2,6‐xylyl; 2b: R = o‐anisyl; 2c: R = benzyl; 2d: R = cyclohexyl; 2e: R = tosylmethyl). Reduction of 2a−2e by NaBH4 in the presence of PPh3 affords the isocyanide‐bridged complexes [(OC)3Fe(μ‐C=N−R)(μ‐dppm)Pt(PPh3)] (3a: R = 2,6‐xylyl; 3b: R = o‐anisyl; 3c: R = benzyl; 3d: R = cyclohexyl; 3e: R = tosylmethyl). Metathesis of 2a−2d with NaI rapidly results in the formation of [(OC)4Fe{μ‐dppm}PtI2(CNR)] (4a−4d), which is slowly transformed under extrusion of CO giving [(OC)2IFe{μ‐dppm}(μ‐CO)PtI(CNR)] (6a: R = 2,6‐xylyl; 6b: R = o‐anisyl; 6c: R = benzyl; 6d: R = cyclohexyl), bearing an iodine ligand at the iron center. Due to this intramolecular iodide migration from Pt to Fe, an FeI d7 fragment interacts with a PtI d9 fragment through a covalent bond. Alternatively, 6a−6d are obtained by stoichiometric treatment of [(CO)3Fe(μ‐I)(μ‐dppm)PtI] (5) with CNR. Single‐crystal X‐ray diffraction studies are performed on 2d, 2e and 3c as well as on 6d. In the solid state, the two metal centers of 2e remain in close contact (3.862 Å), whereas in the case of 2d they are separated by 6.573 Å after cleavage of the metal−metal bond by CNR. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)</abstract><subject lang="en"><genre>keywords</genre><topic>Heterobimetallics</topic><topic>Isocyanide ligands</topic><topic>Metal−metal interactions</topic><topic>Iron</topic><topic>Platinum</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><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>2002</date><detail type="volume"><caption>vol.</caption><number>2002</number></detail><detail type="issue"><caption>no.</caption><number>9</number></detail><extent unit="pages"><start>2419</start><end>2426</end><total>8</total></extent></part></relatedItem><identifier type="istex">D8934F7D0DB4F5512717DA5A7CF247C286FB7D74</identifier><identifier type="DOI">10.1002/1099-0682(200209)2002:9<2419::AID-EJIC2419>3.0.CO;2-U</identifier><identifier type="ArticleID">EJIC2419</identifier><accessCondition type="use and reproduction" contentType="copyright">© 2002 WILEY‐VCH Verlag GmbH & Co. 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