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

Loading...
Thumbnail Image
Date
1987
Authors
van Raaij, Edith U.
Schmulbach, C. David
Editors
Contact
Journal ISSN
Electronic ISSN
ISBN
Bibliographical data
Publisher
Series
URI (citable link)
ArXiv-ID
International patent number
Link to the license
EU project number
Project
Open Access publication
Collections
Restricted until
Title in another language
Research Projects
Organizational Units
Journal Issue
Publication type
Journal article
Publication status
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.
Summary in another language
Subject (DDC)
540 Chemistry
Keywords
Conference
Review
undefined / . - undefined, undefined. - (undefined; undefined)
Cite This
ISO 690VAN 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>
Internal note
xmlui.Submission.submit.DescribeStep.inputForms.label.kops_note_fromSubmitter
Contact
URL of original publication
Test date of URL
Examination date of dissertation
Method of financing
Comment on publication
Alliance license
Corresponding Authors der Uni Konstanz vorhanden
International Co-Authors
Bibliography of Konstanz
Refereed