Synthesis, Reactivity and Molecular Structures of Bis(diphenylphosphanyl)methane‐Bridged Heterobimetallic Iron−Platinum Isocyanide Complexes: Breaking and Formation of Metal−Metal Bonds
Identifieur interne : 000033 ( France/Analysis ); précédent : 000032; suivant : 000034Synthesis, 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)
Url:
DOI: 10.1002/1099-0682(200209)2002:9<2419::AID-EJIC2419>3.0.CO;2-U
Affiliations:
- Allemagne, France
- Bavière, Bourgogne-Franche-Comté, District de Basse-Franconie, Franche-Comté, Sarre (Land)
- Besançon, Sarrebruck, Wurtzbourg
- Université de Wurtzbourg
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ISTEX:D8934F7D0DB4F5512717DA5A7CF247C286FB7D74Le document en format XML
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nuts="2">Franche-Comté</region><settlement type="city">Besançon</settlement></placeName></affiliation><affiliation wicri:level="1"><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="3"><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><placeName><region type="region" nuts="2">Bourgogne-Franche-Comté</region><region type="old region" nuts="2">Franche-Comté</region><settlement type="city">Besançon</settlement></placeName></affiliation></author><author><name sortKey="Crini, Gregorio" sort="Crini, Gregorio" uniqKey="Crini G" first="Grégorio" last="Crini">Grégorio Crini</name><affiliation wicri:level="3"><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><placeName><region type="region" nuts="2">Bourgogne-Franche-Comté</region><region type="old region" nuts="2">Franche-Comté</region><settlement type="city">Besançon</settlement></placeName></affiliation></author><author><name sortKey="Frank, Katja" sort="Frank, Katja" uniqKey="Frank K" first="Katja" last="Frank">Katja Frank</name><affiliation wicri:level="3"><country xml:lang="fr">Allemagne</country><wicri:regionArea>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken</wicri:regionArea><placeName><region type="land" nuts="2">Sarre (Land)</region><settlement type="city">Sarrebruck</settlement></placeName></affiliation></author><author><name sortKey="Sachdev, Hermann" sort="Sachdev, Hermann" uniqKey="Sachdev H" first="Hermann" last="Sachdev">Hermann Sachdev</name><affiliation wicri:level="3"><country xml:lang="fr">Allemagne</country><wicri:regionArea>Institut für Anorganische Chemie der Universität des Saarlandes, Postfach 151150, 66041 Saarbrücken</wicri:regionArea><placeName><region type="land" nuts="2">Sarre (Land)</region><settlement type="city">Sarrebruck</settlement></placeName></affiliation></author><author><name sortKey="Strohmann, Carsten" sort="Strohmann, Carsten" uniqKey="Strohmann C" first="Carsten" last="Strohmann">Carsten Strohmann</name><affiliation wicri:level="4"><country xml:lang="fr">Allemagne</country><wicri:regionArea>Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, 97074 Würzburg</wicri:regionArea><placeName><region type="land" nuts="1">Bavière</region><region type="district" nuts="2">District de Basse-Franconie</region><settlement type="city">Wurtzbourg</settlement></placeName><orgName type="university">Université de Wurtzbourg</orgName></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><affiliations><list><country><li>Allemagne</li><li>France</li></country><region><li>Bavière</li><li>Bourgogne-Franche-Comté</li><li>District de Basse-Franconie</li><li>Franche-Comté</li><li>Sarre (Land)</li></region><settlement><li>Besançon</li><li>Sarrebruck</li><li>Wurtzbourg</li></settlement><orgName><li>Université de Wurtzbourg</li></orgName></list><tree><country name="France"><region name="Bourgogne-Franche-Comté"><name sortKey="Knorr, Michael" sort="Knorr, Michael" uniqKey="Knorr M" first="Michael" last="Knorr">Michael Knorr</name></region><name sortKey="Crini, Gregorio" sort="Crini, Gregorio" uniqKey="Crini G" first="Grégorio" last="Crini">Grégorio Crini</name><name sortKey="Jourdain, Isabelle" sort="Jourdain, Isabelle" uniqKey="Jourdain I" first="Isabelle" last="Jourdain">Isabelle Jourdain</name><name sortKey="Knorr, Michael" sort="Knorr, Michael" uniqKey="Knorr M" first="Michael" last="Knorr">Michael Knorr</name></country><country name="Allemagne"><region name="Sarre (Land)"><name sortKey="Frank, Katja" sort="Frank, Katja" uniqKey="Frank K" first="Katja" last="Frank">Katja Frank</name></region><name sortKey="Sachdev, Hermann" sort="Sachdev, Hermann" uniqKey="Sachdev H" first="Hermann" last="Sachdev">Hermann Sachdev</name><name sortKey="Strohmann, Carsten" sort="Strohmann, Carsten" uniqKey="Strohmann C" first="Carsten" last="Strohmann">Carsten Strohmann</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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