Publikation: ansa-metallocene derivatives : XVII. Racemic and meso diastereomers of group IV metallocene derivatives with symmetrically substituted, dimethylsilanediyl-bridged ligand frameworks. Crystal structure of R,S-Me2Si(3-t-Bu-5-MeC5H2)2ZrCl2
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The formation of racemic and meso diastereomers of the disubstituted ansa-zirconocenes (CH3)2Si(1-C5H3-3-R)2ZrCl2 (R = t-butyl, trimethylsilyl, α,α-dimethylbenzyl and 1-phenylcyclohexyl) from dimethylsilanediyl-bridged, symmetrically substituted bis-cyclopentadienyl dianion derivatives and ZrCl4·2THF has been studied under a variety of conditions. Rac/meso ratios close to 1 were obtained in all cases. Similar product ratios were observed for analogous titanium and hafnium complexes with R = trimethylsilyl. A significant increase in the rac/meso product ratio was observed when an additional substituent was present next to the dimethylsilyl bridge as in (CH3)2Si(1-C5H2-3-R-5-CH3)2ZrCl2 (R = CH(CH3)2, C(CH3)3). It is suggested that intermediates with one η1-bound ring ligand control the stereochemical course of the ansa-metallocene formation. The crystal structure of R,S-(CH3)2Si(1-C5H2-3-C(CH3)3-5-CH3)2ZrCl2 is reported.
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WIESENFELDT, Helga, Annette REINMUTH, Elke BARSTIES, Kaspar EVERTZ, Hans-Herbert BRINTZINGER, 1989. ansa-metallocene derivatives : XVII. Racemic and meso diastereomers of group IV metallocene derivatives with symmetrically substituted, dimethylsilanediyl-bridged ligand frameworks. Crystal structure of R,S-Me2Si(3-t-Bu-5-MeC5H2)2ZrCl2. In: Journal of Organometallic Chemistry. 1989, 369(3), pp. 359-370. ISSN 0022-328X. eISSN 1872-8561. Available under: doi: 10.1016/0022-328X(89)85186-1BibTex
@article{Wiesenfeldt1989ansam-23958, year={1989}, doi={10.1016/0022-328X(89)85186-1}, title={ansa-metallocene derivatives : XVII. Racemic and meso diastereomers of group IV metallocene derivatives with symmetrically substituted, dimethylsilanediyl-bridged ligand frameworks. Crystal structure of R,S-Me<sub>2</sub>Si(3-t-Bu-5-MeC<sub>5</sub>H<sub>2</sub>)<sub>2</sub>ZrCl<sub>2</sub>}, number={3}, volume={369}, issn={0022-328X}, journal={Journal of Organometallic Chemistry}, pages={359--370}, author={Wiesenfeldt, Helga and Reinmuth, Annette and Barsties, Elke and Evertz, Kaspar and Brintzinger, Hans-Herbert} }
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<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/123456789/23958"> <dcterms:title>ansa-metallocene derivatives : XVII. Racemic and meso diastereomers of group IV metallocene derivatives with symmetrically substituted, dimethylsilanediyl-bridged ligand frameworks. Crystal structure of R,S-Me<sub>2</sub>Si(3-t-Bu-5-MeC<sub>5</sub>H<sub>2</sub>)<sub>2</sub>ZrCl<sub>2</sub></dcterms:title> <dc:creator>Reinmuth, Annette</dc:creator> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-08-13T09:20:49Z</dcterms:available> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/> <dc:contributor>Brintzinger, Hans-Herbert</dc:contributor> <dc:contributor>Reinmuth, Annette</dc:contributor> <dc:creator>Wiesenfeldt, Helga</dc:creator> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/23958"/> <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/> <dcterms:issued>1989</dcterms:issued> <dc:contributor>Evertz, Kaspar</dc:contributor> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dc:rights>terms-of-use</dc:rights> <dc:language>eng</dc:language> <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/23958/1/1-s2.0-0022328X89851861Wiesenfeld.pdf"/> <dcterms:abstract xml:lang="eng">The formation of racemic and meso diastereomers of the disubstituted ansa-zirconocenes (CH<sub>3</sub>)<sub>2</sub>Si(1-C<sub>5</sub>H<sub>3</sub>-3-R)<sub>2</sub>ZrCl<sub>2</sub> (R = t-butyl, trimethylsilyl, α,α-dimethylbenzyl and 1-phenylcyclohexyl) from dimethylsilanediyl-bridged, symmetrically substituted bis-cyclopentadienyl dianion derivatives and ZrCl<sub>4</sub>·2THF has been studied under a variety of conditions. Rac/meso ratios close to 1 were obtained in all cases. Similar product ratios were observed for analogous titanium and hafnium complexes with R = trimethylsilyl. A significant increase in the rac/meso product ratio was observed when an additional substituent was present next to the dimethylsilyl bridge as in (CH<sub>3</sub>)<sub>2</sub>Si(1-C<sub>5</sub>H<sub>2</sub>-3-R-5-CH<sub>3</sub>)<sub>2</sub>ZrCl<sub>2</sub> (R = CH(CH<sub>3</sub>)<sub>2</sub>, C(CH<sub>3</sub>)<sub>3</sub>). It is suggested that intermediates with one η<sup>1</sup>-bound ring ligand control the stereochemical course of the ansa-metallocene formation. The crystal structure of R,S-(CH<sub>3</sub>)<sub>2</sub>Si(1-C<sub>5</sub>H<sub>2</sub>-3-C(CH<sub>3</sub>)3-5-CH<sub>3</sub>)<sub>2</sub>ZrCl<sub>2</sub> is reported.</dcterms:abstract> <dc:creator>Evertz, Kaspar</dc:creator> <dc:contributor>Wiesenfeldt, Helga</dc:contributor> <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/23958/1/1-s2.0-0022328X89851861Wiesenfeld.pdf"/> <dcterms:bibliographicCitation>Journal of Organometallic Chemistry ; 369 (1989), 3. - S. 359-370</dcterms:bibliographicCitation> <dc:creator>Brintzinger, Hans-Herbert</dc:creator> <dc:contributor>Barsties, Elke</dc:contributor> <foaf:homepage rdf:resource="http://localhost:8080/"/> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-08-13T09:20:49Z</dc:date> <dc:creator>Barsties, Elke</dc:creator> </rdf:Description> </rdf:RDF>