Heterobinuclear s‐Indacene Rhodium Complexes: Synthesis and Characterization
Identifieur interne : 004E29 ( Istex/Corpus ); précédent : 004E28; suivant : 004E30Heterobinuclear s‐Indacene Rhodium Complexes: Synthesis and Characterization
Auteurs : Christopher Adams ; Cesar Morales Erdejo ; Ver Nica Morales ; Desmond Macleod Arey ; Juan Manuel Manríquez ; Ivonne Chávez ; Alvaro Mu Oz Astro ; Fabien Delpech ; Annie Castel ; Heinz Gornitzka ; Monique Rivière Audet ; Pierre Rivière ; Elies MolinsSource :
- European Journal of Inorganic Chemistry [ 1434-1948 ] ; 2009-02.
English descriptors
Abstract
The monometallic complexes [Cp*M(2,6‐diethyl‐4,8‐dimethyl‐1‐hydroindacenide)] [M = Fe (1), Ru (2), Co (3)] and the bimetallic species anti‐[Cp*M(2,6‐diethyl‐4,8‐dimethyl‐s‐indacenediide)Rh(η4‐cod)] [M = Fe (4a), Ru (5a), Co (6a)] together with syn‐[Cp*Ru(2,6‐diethyl‐4,8‐dimethyl‐s‐indacenediide)Rh(η4‐cod)] (5b) were synthesized and characterized spectroscopically and in the case of complexes 1 and 5b by X‐ray diffraction. 13C and 103Rh NMR spectroscopic studies suggest that the bonding mode of the rhodium center to the s‐indacenediide ligand can be described as an intermediate between η3‐ and η5‐coordination, but closer to an η3 bonding mode when compared to indenyl–Rh complexes. This result was confirmed by the crystal structure of 5b, as evidenced by the slippage of the rhodium atom towards the periphery of the ligand. Cyclic voltammetry studies revealed intermetallic communication through the fused‐ring ligand exclusively in the cases of 5a and 6a.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Url:
DOI: 10.1002/ejic.200800920
Links to Exploration step
ISTEX:AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66Le document en format XML
<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title xml:lang="en">Heterobinuclear s‐Indacene Rhodium Complexes: Synthesis and Characterization</title><author><name sortKey="Adams, Christopher" sort="Adams, Christopher" uniqKey="Adams C" first="Christopher" last="Adams">Christopher Adams</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Morales Erdejo, Cesar" sort="Morales Erdejo, Cesar" uniqKey="Morales Erdejo C" first="Cesar" last="Morales Erdejo">Cesar Morales Erdejo</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Morales, Ver Nica" sort="Morales, Ver Nica" uniqKey="Morales V" first="Ver Nica" last="Morales">Ver Nica Morales</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Macleod Arey, Desmond" sort="Macleod Arey, Desmond" uniqKey="Macleod Arey D" first="Desmond" last="Macleod Arey">Desmond Macleod Arey</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Manriquez, Juan Manuel" sort="Manriquez, Juan Manuel" uniqKey="Manriquez J" first="Juan Manuel" last="Manríquez">Juan Manuel Manríquez</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Chavez, Ivonne" sort="Chavez, Ivonne" uniqKey="Chavez I" first="Ivonne" last="Chávez">Ivonne Chávez</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: ichavez@puc.cl</mods:affiliation></affiliation></author><author><name sortKey="Mu Oz Astro, Alvaro" sort="Mu Oz Astro, Alvaro" uniqKey="Mu Oz Astro A" first="Alvaro" last="Mu Oz Astro">Alvaro Mu Oz Astro</name><affiliation><mods:affiliation>Facultad de Ecología y Recursos naturales, Universidad Andres Bello, Republica 275, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Delpech, Fabien" sort="Delpech, Fabien" uniqKey="Delpech F" first="Fabien" last="Delpech">Fabien Delpech</name><affiliation><mods:affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: fdelpech@insa‐toulouse.fr</mods:affiliation></affiliation></author><author><name sortKey="Castel, Annie" sort="Castel, Annie" uniqKey="Castel A" first="Annie" last="Castel">Annie Castel</name><affiliation><mods:affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Gornitzka, Heinz" sort="Gornitzka, Heinz" uniqKey="Gornitzka H" first="Heinz" last="Gornitzka">Heinz Gornitzka</name><affiliation><mods:affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Riviere Audet, Monique" sort="Riviere Audet, Monique" uniqKey="Riviere Audet M" first="Monique" last="Rivière Audet">Monique Rivière Audet</name><affiliation><mods:affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Riviere, Pierre" sort="Riviere, Pierre" uniqKey="Riviere P" first="Pierre" last="Rivière">Pierre Rivière</name><affiliation><mods:affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Molins, Elies" sort="Molins, Elies" uniqKey="Molins E" first="Elies" last="Molins">Elies Molins</name><affiliation><mods:affiliation>Instituto de Ciencia de los Materiales de Barcelona (ICMAB‐CSIC), Campus UAB, 08193 Bellaterra, Atalunya, Spain</mods:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66</idno><date when="2009" year="2009">2009</date><idno type="doi">10.1002/ejic.200800920</idno><idno type="url">https://api.istex.fr/document/AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">004E29</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a" type="main" xml:lang="en">Heterobinuclear s‐Indacene Rhodium Complexes: Synthesis and Characterization</title><author><name sortKey="Adams, Christopher" sort="Adams, Christopher" uniqKey="Adams C" first="Christopher" last="Adams">Christopher Adams</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Morales Erdejo, Cesar" sort="Morales Erdejo, Cesar" uniqKey="Morales Erdejo C" first="Cesar" last="Morales Erdejo">Cesar Morales Erdejo</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Morales, Ver Nica" sort="Morales, Ver Nica" uniqKey="Morales V" first="Ver Nica" last="Morales">Ver Nica Morales</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Macleod Arey, Desmond" sort="Macleod Arey, Desmond" uniqKey="Macleod Arey D" first="Desmond" last="Macleod Arey">Desmond Macleod Arey</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Manriquez, Juan Manuel" sort="Manriquez, Juan Manuel" uniqKey="Manriquez J" first="Juan Manuel" last="Manríquez">Juan Manuel Manríquez</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Chavez, Ivonne" sort="Chavez, Ivonne" uniqKey="Chavez I" first="Ivonne" last="Chávez">Ivonne Chávez</name><affiliation><mods:affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: ichavez@puc.cl</mods:affiliation></affiliation></author><author><name sortKey="Mu Oz Astro, Alvaro" sort="Mu Oz Astro, Alvaro" uniqKey="Mu Oz Astro A" first="Alvaro" last="Mu Oz Astro">Alvaro Mu Oz Astro</name><affiliation><mods:affiliation>Facultad de Ecología y Recursos naturales, Universidad Andres Bello, Republica 275, Santiago, Chile</mods:affiliation></affiliation></author><author><name sortKey="Delpech, Fabien" sort="Delpech, Fabien" uniqKey="Delpech F" first="Fabien" last="Delpech">Fabien Delpech</name><affiliation><mods:affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: fdelpech@insa‐toulouse.fr</mods:affiliation></affiliation></author><author><name sortKey="Castel, Annie" sort="Castel, Annie" uniqKey="Castel A" first="Annie" last="Castel">Annie Castel</name><affiliation><mods:affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Gornitzka, Heinz" sort="Gornitzka, Heinz" uniqKey="Gornitzka H" first="Heinz" last="Gornitzka">Heinz Gornitzka</name><affiliation><mods:affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Riviere Audet, Monique" sort="Riviere Audet, Monique" uniqKey="Riviere Audet M" first="Monique" last="Rivière Audet">Monique Rivière Audet</name><affiliation><mods:affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Riviere, Pierre" sort="Riviere, Pierre" uniqKey="Riviere P" first="Pierre" last="Rivière">Pierre Rivière</name><affiliation><mods:affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Molins, Elies" sort="Molins, Elies" uniqKey="Molins E" first="Elies" last="Molins">Elies Molins</name><affiliation><mods:affiliation>Instituto de Ciencia de los Materiales de Barcelona (ICMAB‐CSIC), Campus UAB, 08193 Bellaterra, Atalunya, Spain</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="2009-02">2009-02</date><biblScope unit="volume">2009</biblScope><biblScope unit="issue">6</biblScope><biblScope unit="page" from="784">784</biblScope><biblScope unit="page" to="791">791</biblScope></imprint><idno type="ISSN">1434-1948</idno></series><idno type="istex">AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66</idno><idno type="DOI">10.1002/ejic.200800920</idno><idno type="ArticleID">EJIC200800920</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">1434-1948</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Bridging ligands</term><term>Cooperative effects</term><term>Heterometallic complexes</term><term>Metal–metal interactions</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The monometallic complexes [Cp*M(2,6‐diethyl‐4,8‐dimethyl‐1‐hydroindacenide)] [M = Fe (1), Ru (2), Co (3)] and the bimetallic species anti‐[Cp*M(2,6‐diethyl‐4,8‐dimethyl‐s‐indacenediide)Rh(η4‐cod)] [M = Fe (4a), Ru (5a), Co (6a)] together with syn‐[Cp*Ru(2,6‐diethyl‐4,8‐dimethyl‐s‐indacenediide)Rh(η4‐cod)] (5b) were synthesized and characterized spectroscopically and in the case of complexes 1 and 5b by X‐ray diffraction. 13C and 103Rh NMR spectroscopic studies suggest that the bonding mode of the rhodium center to the s‐indacenediide ligand can be described as an intermediate between η3‐ and η5‐coordination, but closer to an η3 bonding mode when compared to indenyl–Rh complexes. This result was confirmed by the crystal structure of 5b, as evidenced by the slippage of the rhodium atom towards the periphery of the ligand. Cyclic voltammetry studies revealed intermetallic communication through the fused‐ring ligand exclusively in the cases of 5a and 6a.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</div></front></TEI><istex><corpusName>wiley</corpusName><author><json:item><name>Christopher Adams</name><affiliations><json:string>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</json:string></affiliations></json:item><json:item><name>Cesar Morales‐Verdejo</name><affiliations><json:string>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</json:string></affiliations></json:item><json:item><name>Verónica Morales</name><affiliations><json:string>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</json:string></affiliations></json:item><json:item><name>Desmond MacLeod‐Carey</name><affiliations><json:string>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</json:string></affiliations></json:item><json:item><name>Juan Manuel Manríquez</name><affiliations><json:string>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</json:string></affiliations></json:item><json:item><name>Ivonne Chávez</name><affiliations><json:string>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</json:string><json:string>E-mail: ichavez@puc.cl</json:string></affiliations></json:item><json:item><name>Alvaro Muñoz‐Castro</name><affiliations><json:string>Facultad de Ecología y Recursos naturales, Universidad Andres Bello, Republica 275, Santiago, Chile</json:string></affiliations></json:item><json:item><name>Fabien Delpech</name><affiliations><json:string>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</json:string><json:string>E-mail: fdelpech@insa‐toulouse.fr</json:string></affiliations></json:item><json:item><name>Annie Castel</name><affiliations><json:string>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</json:string></affiliations></json:item><json:item><name>Heinz Gornitzka</name><affiliations><json:string>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</json:string></affiliations></json:item><json:item><name>Monique Rivière‐Baudet</name><affiliations><json:string>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</json:string></affiliations></json:item><json:item><name>Pierre Rivière</name><affiliations><json:string>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</json:string></affiliations></json:item><json:item><name>Elies Molins</name><affiliations><json:string>Instituto de Ciencia de los Materiales de Barcelona (ICMAB‐CSIC), Campus UAB, 08193 Bellaterra, Atalunya, Spain</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>Heterometallic complexes</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Cooperative effects</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Bridging ligands</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Metal–metal interactions</value></json:item></subject><articleId><json:string>EJIC200800920</json:string></articleId><language><json:string>eng</json:string></language><qualityIndicators><score>6.68</score><pdfVersion>1.3</pdfVersion><pdfPageSize>593 x 794 pts</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>4</keywordCount><abstractCharCount>1032</abstractCharCount><pdfWordCount>6192</pdfWordCount><pdfCharCount>37293</pdfCharCount><pdfPageCount>8</pdfPageCount><abstractWordCount>140</abstractWordCount></qualityIndicators><title>Heterobinuclear s‐Indacene Rhodium Complexes: Synthesis and Characterization</title><genre.original><json:string>bookReview</json:string></genre.original><genre><json:string>book-reviews</json:string></genre><host><volume>2009</volume><publisherId><json:string>EJIC</json:string></publisherId><pages><total>8</total><last>791</last><first>784</first></pages><issn><json:string>1434-1948</json:string></issn><issue>6</issue><subject><json:item><value>Full Paper</value></json:item></subject><genre><json:string>journal</json:string></genre><language><json:string>unknown</json:string></language><eissn><json:string>1099-0682</json:string></eissn><title>European Journal of Inorganic Chemistry</title><doi><json:string>10.1002/(ISSN)1099-0682c</json:string></doi></host><publicationDate>2009</publicationDate><copyrightDate>2009</copyrightDate><doi><json:string>10.1002/ejic.200800920</json:string></doi><id>AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66</id><score>1</score><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66/fulltext/pdf</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">Heterobinuclear s‐Indacene Rhodium Complexes: Synthesis and Characterization</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><availability><p>WILEY</p></availability><date>2009</date></publicationStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a" type="main" xml:lang="en">Heterobinuclear s‐Indacene Rhodium Complexes: Synthesis and Characterization</title><author><persName><forename type="first">Christopher</forename><surname>Adams</surname></persName><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation></author><author><persName><forename type="first">Cesar</forename><surname>Morales‐Verdejo</surname></persName><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation></author><author><persName><forename type="first">Verónica</forename><surname>Morales</surname></persName><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation></author><author><persName><forename type="first">Desmond</forename><surname>MacLeod‐Carey</surname></persName><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation></author><author><persName><forename type="first">Juan Manuel</forename><surname>Manríquez</surname></persName><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation></author><author><persName><forename type="first">Ivonne</forename><surname>Chávez</surname></persName><email>ichavez@puc.cl</email><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation></author><author><persName><forename type="first">Alvaro</forename><surname>Muñoz‐Castro</surname></persName><affiliation>Facultad de Ecología y Recursos naturales, Universidad Andres Bello, Republica 275, Santiago, Chile</affiliation></author><author><persName><forename type="first">Fabien</forename><surname>Delpech</surname></persName><email>fdelpech@insa‐toulouse.fr</email><affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</affiliation></author><author><persName><forename type="first">Annie</forename><surname>Castel</surname></persName><affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</affiliation></author><author><persName><forename type="first">Heinz</forename><surname>Gornitzka</surname></persName><affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</affiliation></author><author><persName><forename type="first">Monique</forename><surname>Rivière‐Baudet</surname></persName><affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</affiliation></author><author><persName><forename type="first">Pierre</forename><surname>Rivière</surname></persName><affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</affiliation></author><author><persName><forename type="first">Elies</forename><surname>Molins</surname></persName><affiliation>Instituto de Ciencia de los Materiales de Barcelona (ICMAB‐CSIC), Campus UAB, 08193 Bellaterra, Atalunya, Spain</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="2009-02"></date><biblScope unit="volume">2009</biblScope><biblScope unit="issue">6</biblScope><biblScope unit="page" from="784">784</biblScope><biblScope unit="page" to="791">791</biblScope></imprint></monogr><idno type="istex">AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66</idno><idno type="DOI">10.1002/ejic.200800920</idno><idno type="ArticleID">EJIC200800920</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2009</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The monometallic complexes [Cp*M(2,6‐diethyl‐4,8‐dimethyl‐1‐hydroindacenide)] [M = Fe (1), Ru (2), Co (3)] and the bimetallic species anti‐[Cp*M(2,6‐diethyl‐4,8‐dimethyl‐s‐indacenediide)Rh(η4‐cod)] [M = Fe (4a), Ru (5a), Co (6a)] together with syn‐[Cp*Ru(2,6‐diethyl‐4,8‐dimethyl‐s‐indacenediide)Rh(η4‐cod)] (5b) were synthesized and characterized spectroscopically and in the case of complexes 1 and 5b by X‐ray diffraction. 13C and 103Rh NMR spectroscopic studies suggest that the bonding mode of the rhodium center to the s‐indacenediide ligand can be described as an intermediate between η3‐ and η5‐coordination, but closer to an η3 bonding mode when compared to indenyl–Rh complexes. This result was confirmed by the crystal structure of 5b, as evidenced by the slippage of the rhodium atom towards the periphery of the ligand. Cyclic voltammetry studies revealed intermetallic communication through the fused‐ring ligand exclusively in the cases of 5a and 6a.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</p></abstract><abstract xml:lang="en" style="graphical"><p>Heterobinuclear s‐indacene rhodium complexes were recently synthesized, bearing secondary metallic fragments such as Cp*M (M = Fe, Co, and Ru). An unprecedented complex such as the syn‐isomer of Cp*Ru[s‐indacenediide]Rh(cod) was also formed and identified by X‐ray diffraction techniques.</p></abstract><textClass xml:lang="en"><keywords scheme="keyword"><list><head>keywords</head><item><term>Heterometallic complexes</term></item><item><term>Cooperative effects</term></item><item><term>Bridging ligands</term></item><item><term>Metal–metal interactions</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="2008-09-15">Received</change><change when="2009-02">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66/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="60"><doi origin="wiley" registered="yes">10.1002/ejic.v2009:6</doi><numberingGroup><numbering type="journalVolume" number="2009">2009</numbering><numbering type="journalIssue">6</numbering></numberingGroup><coverDate startDate="2009-02">February 2009</coverDate></publicationMeta><publicationMeta level="unit" type="bookReview" position="14" status="forIssue"><doi origin="wiley" registered="yes">10.1002/ejic.200800920</doi><idGroup><id type="unit" value="EJIC200800920"></id></idGroup><countGroup><count type="pageTotal" number="8"></count></countGroup><titleGroup><title type="articleCategory">Full Paper</title><title type="tocHeading1">Full Papers</title><title type="tocHeading2">Heterobinuclear Rhodium Complexes</title></titleGroup><copyright ownership="publisher">Copyright © 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</copyright><eventGroup><event type="manuscriptReceived" date="2008-09-15"></event><event type="firstOnline" date="2009-01-16"></event><event type="publishedOnlineFinalForm" date="2009-02-10"></event><event type="xmlConverted" agent="Converter:JWSART34_TO_WML3G version:2.3.6 mode:FullText source:FullText result:FullText mathml2tex" date="2010-04-19"></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">784</numbering><numbering type="pageLast">791</numbering></numberingGroup><objectNameGroup><objectName elementName="figure">Scheme</objectName></objectNameGroup><linkGroup><link type="toTypesetVersion" href="file:EJIC.EJIC200800920.pdf"></link></linkGroup></publicationMeta><contentMeta><countGroup><count type="figureTotal" number="2"></count><count type="tableTotal" number="1"></count><count type="referenceTotal" number="27"></count></countGroup><titleGroup><title type="main" xml:lang="en">Heterobinuclear <i>s</i>‐Indacene Rhodium Complexes: Synthesis and Characterization</title><title type="short" xml:lang="en">Heterobinuclear <i>s</i>‐Indacene Rhodium Complexes</title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Christopher</givenNames><familyName>Adams</familyName></personName></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Cesar</givenNames><familyName>Morales‐Verdejo</familyName></personName></creator><creator xml:id="au3" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Verónica</givenNames><familyName>Morales</familyName></personName></creator><creator xml:id="au4" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Desmond</givenNames><familyName>MacLeod‐Carey</familyName></personName></creator><creator xml:id="au5" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Juan Manuel</givenNames><familyName>Manríquez</familyName></personName></creator><creator xml:id="au6" creatorRole="author" affiliationRef="#af1"><personName><givenNames>Ivonne</givenNames><familyName>Chávez</familyName></personName><contactDetails><email>ichavez@puc.cl</email></contactDetails></creator><creator xml:id="au7" creatorRole="author" affiliationRef="#af2"><personName><givenNames>Alvaro</givenNames><familyName>Muñoz‐Castro</familyName></personName></creator><creator xml:id="au8" creatorRole="author" affiliationRef="#af3"><personName><givenNames>Fabien</givenNames><familyName>Delpech</familyName></personName><contactDetails><email normalForm="fdelpech@insa-toulouse.fr">fdelpech@insa‐toulouse.fr</email></contactDetails></creator><creator xml:id="au9" creatorRole="author" affiliationRef="#af3"><personName><givenNames>Annie</givenNames><familyName>Castel</familyName></personName></creator><creator xml:id="au10" creatorRole="author" affiliationRef="#af3"><personName><givenNames>Heinz</givenNames><familyName>Gornitzka</familyName></personName></creator><creator xml:id="au11" creatorRole="author" affiliationRef="#af3"><personName><givenNames>Monique</givenNames><familyName>Rivière‐Baudet</familyName></personName></creator><creator xml:id="au12" creatorRole="author" affiliationRef="#af3"><personName><givenNames>Pierre</givenNames><familyName>Rivière</familyName></personName></creator><creator xml:id="au13" creatorRole="author" affiliationRef="#af4"><personName><givenNames>Elies</givenNames><familyName>Molins</familyName></personName></creator></creators><affiliationGroup><affiliation xml:id="af1" countryCode="CL" type="organization"><unparsedAffiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</unparsedAffiliation></affiliation><affiliation xml:id="af2" countryCode="CL" type="organization"><unparsedAffiliation>Facultad de Ecología y Recursos naturales, Universidad Andres Bello, Republica 275, Santiago, Chile</unparsedAffiliation></affiliation><affiliation xml:id="af3" countryCode="FR" type="organization"><unparsedAffiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</unparsedAffiliation></affiliation><affiliation xml:id="af4" countryCode="ES" type="organization"><unparsedAffiliation>Instituto de Ciencia de los Materiales de Barcelona (ICMAB‐CSIC), Campus UAB, 08193 Bellaterra, Atalunya, Spain</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">Heterometallic complexes</keyword><keyword xml:id="kwd2">Cooperative effects</keyword><keyword xml:id="kwd3">Bridging ligands</keyword><keyword xml:id="kwd4">Metal–metal interactions</keyword></keywordGroup><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>The monometallic complexes [Cp*M(2,6‐diethyl‐4,8‐dimethyl‐1‐hydroindacenide)] [M = Fe (<b>1</b>), Ru (<b>2</b>), Co (<b>3</b>)] and the bimetallic species <i>anti</i>‐[Cp*M(2,6‐diethyl‐4,8‐dimethyl‐<i>s</i>‐indacenediide)Rh(η<sup>4</sup>‐cod)] [M = Fe (<b>4a</b>), Ru (<b>5a</b>), Co (<b>6a</b>)] together with <i>syn</i>‐[Cp*Ru(2,6‐diethyl‐4,8‐dimethyl‐<i>s</i>‐indacenediide)Rh(η<sup>4</sup>‐cod)] (<b>5b</b>) were synthesized and characterized spectroscopically and in the case of complexes <b>1</b> and <b>5b</b> by X‐ray diffraction. <sup>13</sup>C and <sup>103</sup>Rh NMR spectroscopic studies suggest that the bonding mode of the rhodium center to the <i>s</i>‐indacenediide ligand can be described as an intermediate between η<sup>3</sup>‐ and η<sup>5</sup>‐coordination, but closer to an η<sup>3</sup> bonding mode when compared to indenyl–Rh complexes. This result was confirmed by the crystal structure of <b>5b</b>, as evidenced by the slippage of the rhodium atom towards the periphery of the ligand. Cyclic voltammetry studies revealed intermetallic communication through the fused‐ring ligand exclusively in the cases of <b>5a</b> and <b>6a</b>.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</p></abstract><abstract type="graphical" xml:lang="en"><p>Heterobinuclear <i>s</i>‐indacene rhodium complexes were recently synthesized, bearing secondary metallic fragments such as Cp*M (M = Fe, Co, and Ru). An unprecedented complex such as the <i>syn</i>‐isomer of Cp*Ru[<i>s</i>‐indacenediide]Rh(cod) was also formed and identified by X‐ray diffraction techniques. <blockFixed type="graphic"><mediaResourceGroup><mediaResource alt="image" eRights="yes" copyright="WILEY-VCH" href="urn:x-wiley:14341948:media:EJIC200800920:fig000"></mediaResource><mediaResource alt="thumbnail image" rendition="webLoRes" mimeType="image/gif" href=""></mediaResource><mediaResource alt="original image" rendition="webOriginal" mimeType="image/jpeg" href=""></mediaResource><mediaResource alt="magnified image" rendition="webHiRes" mimeType="image/jpeg" href=""></mediaResource></mediaResourceGroup></blockFixed></p></abstract></abstractGroup></contentMeta></header></component></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Heterobinuclear s‐Indacene Rhodium Complexes: Synthesis and Characterization</title></titleInfo><titleInfo type="abbreviated" lang="en"><title>Heterobinuclear s‐Indacene Rhodium Complexes</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>Heterobinuclear</title></titleInfo><name type="personal"><namePart type="given">Christopher</namePart><namePart type="family">Adams</namePart><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Cesar</namePart><namePart type="family">Morales‐Verdejo</namePart><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Verónica</namePart><namePart type="family">Morales</namePart><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Desmond</namePart><namePart type="family">MacLeod‐Carey</namePart><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Juan Manuel</namePart><namePart type="family">Manríquez</namePart><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Ivonne</namePart><namePart type="family">Chávez</namePart><affiliation>Departamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306 Correo 22, Santiago, Chile</affiliation><affiliation>E-mail: ichavez@puc.cl</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Alvaro</namePart><namePart type="family">Muñoz‐Castro</namePart><affiliation>Facultad de Ecología y Recursos naturales, Universidad Andres Bello, Republica 275, Santiago, Chile</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Fabien</namePart><namePart type="family">Delpech</namePart><affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</affiliation><affiliation>E-mail: fdelpech@insa‐toulouse.fr</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Annie</namePart><namePart type="family">Castel</namePart><affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Heinz</namePart><namePart type="family">Gornitzka</namePart><affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Monique</namePart><namePart type="family">Rivière‐Baudet</namePart><affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Pierre</namePart><namePart type="family">Rivière</namePart><affiliation>Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, Université Paul Sabatier, 31062 Toulouse, Cedex 9, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Elies</namePart><namePart type="family">Molins</namePart><affiliation>Instituto de Ciencia de los Materiales de Barcelona (ICMAB‐CSIC), Campus UAB, 08193 Bellaterra, Atalunya, Spain</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="book-reviews" displayLabel="bookReview"></genre><originInfo><publisher>WILEY‐VCH Verlag</publisher><place><placeTerm type="text">Weinheim</placeTerm></place><dateIssued encoding="w3cdtf">2009-02</dateIssued><dateCaptured encoding="w3cdtf">2008-09-15</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">2</extent><extent unit="tables">1</extent><extent unit="references">27</extent></physicalDescription><abstract lang="en">The monometallic complexes [Cp*M(2,6‐diethyl‐4,8‐dimethyl‐1‐hydroindacenide)] [M = Fe (1), Ru (2), Co (3)] and the bimetallic species anti‐[Cp*M(2,6‐diethyl‐4,8‐dimethyl‐s‐indacenediide)Rh(η4‐cod)] [M = Fe (4a), Ru (5a), Co (6a)] together with syn‐[Cp*Ru(2,6‐diethyl‐4,8‐dimethyl‐s‐indacenediide)Rh(η4‐cod)] (5b) were synthesized and characterized spectroscopically and in the case of complexes 1 and 5b by X‐ray diffraction. 13C and 103Rh NMR spectroscopic studies suggest that the bonding mode of the rhodium center to the s‐indacenediide ligand can be described as an intermediate between η3‐ and η5‐coordination, but closer to an η3 bonding mode when compared to indenyl–Rh complexes. This result was confirmed by the crystal structure of 5b, as evidenced by the slippage of the rhodium atom towards the periphery of the ligand. Cyclic voltammetry studies revealed intermetallic communication through the fused‐ring ligand exclusively in the cases of 5a and 6a.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</abstract><abstract type="graphical" lang="en">Heterobinuclear s‐indacene rhodium complexes were recently synthesized, bearing secondary metallic fragments such as Cp*M (M = Fe, Co, and Ru). An unprecedented complex such as the syn‐isomer of Cp*Ru[s‐indacenediide]Rh(cod) was also formed and identified by X‐ray diffraction techniques.</abstract><subject lang="en"><genre>keywords</genre><topic>Heterometallic complexes</topic><topic>Cooperative effects</topic><topic>Bridging ligands</topic><topic>Metal–metal interactions</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>2009</date><detail type="volume"><caption>vol.</caption><number>2009</number></detail><detail type="issue"><caption>no.</caption><number>6</number></detail><extent unit="pages"><start>784</start><end>791</end><total>8</total></extent></part></relatedItem><identifier type="istex">AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66</identifier><identifier type="DOI">10.1002/ejic.200800920</identifier><identifier type="ArticleID">EJIC200800920</identifier><accessCondition type="use and reproduction" contentType="copyright">Copyright © 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</accessCondition><recordInfo><recordContentSource>WILEY</recordContentSource><recordOrigin>WILEY‐VCH Verlag</recordOrigin></recordInfo></mods></metadata><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
EXPLOR_STEP=$WICRI_ROOT/Ticri/CIDE/explor/HapticV1/Data/Istex/Corpus
HfdSelect -h $EXPLOR_STEP/biblio.hfd -nk 004E29 | SxmlIndent | more
Ou
HfdSelect -h $EXPLOR_AREA/Data/Istex/Corpus/biblio.hfd -nk 004E29 | SxmlIndent | more
Pour mettre un lien sur cette page dans le réseau Wicri
{{Explor lien
|wiki= Ticri/CIDE
|area= HapticV1
|flux= Istex
|étape= Corpus
|type= RBID
|clé= ISTEX:AD0B94E29F5BB85FD9D55E01E3D93BA8674AFB66
|texte= Heterobinuclear s‐Indacene Rhodium Complexes: Synthesis and Characterization
}}
| This area was generated with Dilib version V0.6.23. |  |