Equilibria and kinetics in the CO-induced, reversible disproportionation of ((C5H5)2TiCl)2 to (C5H5)2TiCl2 and (C5H52Ti(CO)2. An IR study at elevated CO gas pressures

van Raaij, Edith U.; Schmulbach, C. David; Brintzinger, Hans-Herbert

Equilibria and kinetics in the CO-induced, reversible disproportionation of ((C₅H₅)₂TiCl)₂ to (C₅H₅)₂TiCl₂ and (C₅H₅₂Ti(CO)₂. An IR study at elevated CO gas pressures

Files

Brintzinger_240508.pdf(464.87 KB)

Date

1987

Authors

van Raaij, Edith U.

Schmulbach, C. David

Brintzinger, Hans-Herbert

Publication type

Journal article

Published in

Journal of Organometallic Chemistry ; 328 (1987), 3. - pp. 275-285. - ISSN 0022-328X. - eISSN 1872-8561

Abstract

IR studies of toluene solutions of ((C₅H₅)₂TiCl)₂ under elevated CO pressures indicate the formation of a carbonyl complex, probably (C₅H₅)₂Ti(CO)Cl, with ν(CO) 2068 cm⁻. This species predominates at CO pressures above 100 bar, and is reasonably stable at temperatures around −30°C. At higher temperatures, disproportionation to (C₅H₅)₂Ti(CO)₂ and (C₅H₅)₂TiCl₂ occurs. This disproportionation is reversible; at +30°C and 1 bar of CO, roughly equal concentrations of ((C₅H₅)₂TiCl)₂ and of dicarbonyl and dichloride products are in equilibrium with each other. Practically complete formation of these products occurs at CO pressures above 10 bar. Rate laws and reaction mechanisms have been studied for the disproportionation reaction and for its reverse, the comproportionation of (C₅H₅)₂Ti(CO)₂ and (C₅H₅)₂TiCl₂ to ((C₅H₅)₂TiCl)₂, which predominates at lower CO pressures.

Subject (DDC)

540 Chemistry

Cite This

ISO 690

VAN RAAIJ, Edith U., C. David SCHMULBACH, Hans-Herbert BRINTZINGER, 1987. Equilibria and kinetics in the CO-induced, reversible disproportionation of ((C₅H₅)₂TiCl)₂ to (C₅H₅)₂TiCl₂ and (C₅H₅₂Ti(CO)₂. An IR study at elevated CO gas pressures. In: Journal of Organometallic Chemistry. 328(3), pp. 275-285. ISSN 0022-328X. eISSN 1872-8561. Available under: doi: 10.1016/0022-328X(87)80245-0

BibTex

@article{vanRaaij1987Equil-24050,
  year={1987},
  doi={10.1016/0022-328X(87)80245-0},
  title={Equilibria and kinetics in the CO-induced, reversible disproportionation of ((C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>TiCl)<sub>2</sub> to (C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>TiCl<sub>2</sub> and (C<sub>5</sub>H<sub>52</sub>Ti(CO)<sub>2</sub>. An IR study at elevated CO gas pressures},
  number={3},
  volume={328},
  issn={0022-328X},
  journal={Journal of Organometallic Chemistry},
  pages={275--285},
  author={van Raaij, Edith U. and Schmulbach, C. David and Brintzinger, Hans-Herbert}
}

RDF

<rdf:RDF
    xmlns:dcterms="http://purl.org/dc/terms/"
    xmlns:dc="http://purl.org/dc/elements/1.1/"
    xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#"
    xmlns:bibo="http://purl.org/ontology/bibo/"
    xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#"
    xmlns:foaf="http://xmlns.com/foaf/0.1/"
    xmlns:void="http://rdfs.org/ns/void#"
    xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > 
  <rdf:Description rdf:about="https://kops.uni-konstanz.de/server/rdf/resource/123456789/24050">
    <dc:creator>Brintzinger, Hans-Herbert</dc:creator>
    <dc:creator>van Raaij, Edith U.</dc:creator>
    <dc:contributor>van Raaij, Edith U.</dc:contributor>
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
    <dc:contributor>Brintzinger, Hans-Herbert</dc:contributor>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-08-16T12:19:32Z</dc:date>
    <dc:rights>terms-of-use</dc:rights>
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/24050/2/Brintzinger_240508.pdf"/>
    <dc:language>eng</dc:language>
    <dcterms:abstract xml:lang="eng">IR studies of toluene solutions of ((C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;TiCl)&lt;sub&gt;2&lt;/sub&gt; under elevated CO pressures indicate the formation of a carbonyl complex, probably (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Ti(CO)Cl, with ν(CO) 2068 cm&lt;sup&gt;−&lt;/sup&gt;. This species predominates at CO pressures above 100 bar, and is reasonably stable at temperatures around −30°C. At higher temperatures, disproportionation to (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Ti(CO)&lt;sub&gt;2&lt;/sub&gt; and (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;TiCl&lt;sub&gt;2&lt;/sub&gt; occurs. This disproportionation is reversible; at +30°C and 1 bar of CO, roughly equal concentrations of ((C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;TiCl)&lt;sub&gt;2&lt;/sub&gt; and of dicarbonyl and dichloride products are in equilibrium with each other. Practically complete formation of these products occurs at CO pressures above 10 bar. Rate laws and reaction mechanisms have been studied for the disproportionation reaction and for its reverse, the comproportionation of (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Ti(CO)&lt;sub&gt;2&lt;/sub&gt; and (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;TiCl&lt;sub&gt;2&lt;/sub&gt; to ((C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;TiCl)&lt;sub&gt;2&lt;/sub&gt;, which predominates at lower CO pressures.</dcterms:abstract>
    <dc:contributor>Schmulbach, C. David</dc:contributor>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/24050"/>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dcterms:bibliographicCitation>Journal of Organometallic Chemistry ; 328 (1987), 3. - S. 275-285</dcterms:bibliographicCitation>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/24050/2/Brintzinger_240508.pdf"/>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-08-16T12:19:32Z</dcterms:available>
    <dcterms:issued>1987</dcterms:issued>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:creator>Schmulbach, C. David</dc:creator>
    <dcterms:title>Equilibria and kinetics in the CO-induced, reversible disproportionation of ((C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;TiCl)&lt;sub&gt;2&lt;/sub&gt; to (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;TiCl&lt;sub&gt;2&lt;/sub&gt; and (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;52&lt;/sub&gt;Ti(CO)&lt;sub&gt;2&lt;/sub&gt;. An IR study at elevated CO gas pressures</dcterms:title>
  </rdf:Description>
</rdf:RDF>