Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds
Identifieur interne : 001529 ( Istex/Curation ); précédent : 001528; suivant : 001530Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds
Auteurs : Michael Knorr [France] ; Isabelle Jourdain [France] ; Grégorio Crini [France] ; Katja Frank [Allemagne] ; Hermann Sachdev [Allemagne] ; Carsten Strohmann [Allemagne]Source :
- European Journal of Inorganic Chemistry [ 1434-1948 ] ; 2002-09.
Descripteurs français
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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michael.knorr@univ‐fcomte.fr</mods:affiliation><country wicri:rule="url">France</country></affiliation></author><author><name sortKey="Jourdain, Isabelle" sort="Jourdain, Isabelle" uniqKey="Jourdain I" first="Isabelle" last="Jourdain">Isabelle Jourdain</name><affiliation wicri:level="1"><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><country xml:lang="fr">France</country><wicri:regionArea>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex</wicri:regionArea></affiliation></author><author><name sortKey="Crini, Gregorio" sort="Crini, Gregorio" uniqKey="Crini G" first="Grégorio" last="Crini">Grégorio Crini</name><affiliation wicri:level="1"><mods:affiliation>Laboratoire de Chimie des Matériaux et Interfaces, Université de 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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><country xml:lang="fr">France</country><wicri:regionArea>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex</wicri:regionArea></affiliation><affiliation wicri:level="1"><mods:affiliation>E-mail: michael.knorr@univ‐fcomte.fr</mods:affiliation><country wicri:rule="url">France</country></affiliation></author><author><name sortKey="Jourdain, Isabelle" sort="Jourdain, Isabelle" uniqKey="Jourdain I" first="Isabelle" last="Jourdain">Isabelle Jourdain</name><affiliation wicri:level="1"><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><country xml:lang="fr">France</country><wicri:regionArea>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex</wicri:regionArea></affiliation></author><author><name sortKey="Crini, Gregorio" sort="Crini, Gregorio" uniqKey="Crini G" first="Grégorio" last="Crini">Grégorio Crini</name><affiliation wicri:level="1"><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><country xml:lang="fr">France</country><wicri:regionArea>Laboratoire de Chimie des Matériaux et Interfaces, Université de Franche‐Comté, Faculté des Sciences et des Techniques, 16, Route de Gray, 25030 Besançon Cedex</wicri:regionArea></affiliation></author><author><name sortKey="Frank, Katja" sort="Frank, Katja" uniqKey="Frank K" first="Katja" last="Frank">Katja Frank</name><affiliation wicri:level="1"><mods:affiliation>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken, Germany</mods:affiliation><country xml:lang="fr">Allemagne</country><wicri:regionArea>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken</wicri:regionArea></affiliation></author><author><name sortKey="Sachdev, Hermann" sort="Sachdev, Hermann" uniqKey="Sachdev H" first="Hermann" last="Sachdev">Hermann Sachdev</name><affiliation wicri:level="1"><mods:affiliation>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken, Germany</mods:affiliation><country xml:lang="fr">Allemagne</country><wicri:regionArea>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken</wicri:regionArea></affiliation></author><author><name sortKey="Strohmann, Carsten" sort="Strohmann, Carsten" uniqKey="Strohmann C" first="Carsten" last="Strohmann">Carsten Strohmann</name><affiliation wicri:level="1"><mods:affiliation>Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, 97074 Würzburg, Germany</mods:affiliation><country xml:lang="fr">Allemagne</country><wicri:regionArea>Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, 97074 Würzburg</wicri:regionArea></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><keywords scheme="Wicri" type="topic" xml:lang="fr"><term>Fer</term><term>Platine</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></record>Pour manipuler ce document sous Unix (Dilib)
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