Activation of dimethyl zirconocene by methylaluminoxane (MAO)-size estimate for Me-MAO- anions by pulsed field-gradient NMR

Kurzanzeige
dc.contributor.authorBabushkin, Dmitrii E.deu
dc.contributor.authorBrintzinger, Hans-Herbert
dc.date.accessioned2013-06-20T15:04:06Zdeu
dc.date.available2013-06-20T15:04:06Zdeu
dc.date.issued2002
dc.description.abstractIn a study of the reaction system MAO/(C5H5)2ZrMe2, the size of the ion pair [(C5H5)2Zr(μ-Me)2AlMe2]+ [Me-MAO]- was determined by pulsed field-gradient NMR of its cationic moiety. A mean effective hydrodynamic radius of 12.2−12.5 Å, determined from diffusion rates in benzene solution at different zirconocene and MAO concentrations, indicates that the ion pair remains associated even at the lowest concentrations studied. At elevated concentrations, aggregation to ion quadruples or higher aggregates is indicated by an apparent size increase and by shifts of the C5H5 and Me 1H NMR signals. The equilibrium constant for the reaction [(C5H5)2ZrMe+***Me-MAO-] + 1/2Al2Me6 [(C5H5)2Zr(μ-Me)2AlMe2]+ [Me-MAO]- changes at different Al/Zr ratios; this indicates that MAO contains various species that produce Me-MAO- anions with different Lewis basicities. The volume of the Me-MAO- anion suggests that it contains 150−200 Al atoms.eng
dc.description.versionpublished
dc.identifier.citationJournal of American Chemical Society ; 124 (2002), 43. - S. 12869-12873deu
dc.identifier.doi10.1021/ja020646mdeu
dc.identifier.urihttp://kops.uni-konstanz.de/handle/123456789/23717
dc.language.isoengdeu
dc.legacy.dateIssued2013-06-20deu
dc.rightsterms-of-usedeu
dc.rights.urihttps://rightsstatements.org/page/InC/1.0/deu
dc.subject.ddc540deu
dc.titleActivation of dimethyl zirconocene by methylaluminoxane (MAO)-size estimate for Me-MAO<sup>-</sup> anions by pulsed field-gradient NMReng
dc.typeJOURNAL_ARTICLEdeu
dspace.entity.typePublication
kops.citation.bibtex
@article{Babushkin2002Activ-23717,
  year={2002},
  doi={10.1021/ja020646m},
  title={Activation of dimethyl zirconocene by methylaluminoxane (MAO)-size estimate for Me-MAO<sup>-</sup> anions by pulsed field-gradient NMR},
  number={43},
  volume={124},
  issn={0002-7863},
  journal={Journal of the American Chemical Society},
  pages={12869--12873},
  author={Babushkin, Dmitrii E. and Brintzinger, Hans-Herbert}
}
kops.citation.iso690BABUSHKIN, Dmitrii E., Hans-Herbert BRINTZINGER, 2002. Activation of dimethyl zirconocene by methylaluminoxane (MAO)-size estimate for Me-MAO- anions by pulsed field-gradient NMR. In: Journal of the American Chemical Society. 2002, 124(43), pp. 12869-12873. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja020646mdeu
kops.citation.iso690BABUSHKIN, Dmitrii E., Hans-Herbert BRINTZINGER, 2002. Activation of dimethyl zirconocene by methylaluminoxane (MAO)-size estimate for Me-MAO- anions by pulsed field-gradient NMR. In: Journal of the American Chemical Society. 2002, 124(43), pp. 12869-12873. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja020646meng
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    <dcterms:abstract xml:lang="eng">In a study of the reaction system MAO/(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrMe&lt;sub&gt;2&lt;/sub&gt;, the size of the ion pair [(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Zr(μ-Me)&lt;sub&gt;2&lt;/sub&gt;AlMe&lt;sub&gt;2&lt;/sub&gt;]&lt;sup&gt;+&lt;/sup&gt; [Me-MAO]&lt;sup&gt;-&lt;/sup&gt; was determined by pulsed field-gradient NMR of its cationic moiety. A mean effective hydrodynamic radius of 12.2−12.5 Å, determined from diffusion rates in benzene solution at different zirconocene and MAO concentrations, indicates that the ion pair remains associated even at the lowest concentrations studied. At elevated concentrations, aggregation to ion quadruples or higher aggregates is indicated by an apparent size increase and by shifts of the C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt; and Me &lt;sup&gt;1&lt;/sup&gt;H NMR signals. The equilibrium constant for the reaction [(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;ZrMe&lt;sup&gt;+&lt;/sup&gt;***Me-MAO&lt;sup&gt;-&lt;/sup&gt;] + &lt;sup&gt;1&lt;/sup&gt;/&lt;sub&gt;2&lt;/sub&gt;Al&lt;sub&gt;2&lt;/sub&gt;Me&lt;sub&gt;6&lt;/sub&gt; [(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;Zr(μ-Me)&lt;sub&gt;2&lt;/sub&gt;AlMe&lt;sub&gt;2&lt;/sub&gt;]&lt;sup&gt;+&lt;/sup&gt; [Me-MAO]&lt;sup&gt;-&lt;/sup&gt; changes at different Al/Zr ratios; this indicates that MAO contains various species that produce Me-MAO&lt;sup&gt;-&lt;/sup&gt; anions with different Lewis basicities. The volume of the Me-MAO&lt;sup&gt;-&lt;/sup&gt; anion suggests that it contains 150−200 Al atoms.</dcterms:abstract>
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kops.identifier.nbnurn:nbn:de:bsz:352-237172deu
kops.sourcefieldJournal of the American Chemical Society. 2002, <b>124</b>(43), pp. 12869-12873. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja020646mdeu
kops.sourcefield.plainJournal of the American Chemical Society. 2002, 124(43), pp. 12869-12873. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja020646mdeu
kops.sourcefield.plainJournal of the American Chemical Society. 2002, 124(43), pp. 12869-12873. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja020646meng
kops.submitter.emailoleg.kozlov@uni-konstanz.dedeu
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source.bibliographicInfo.fromPage12869
source.bibliographicInfo.issue43
source.bibliographicInfo.toPage12873
source.bibliographicInfo.volume124
source.identifier.eissn1520-5126deu
source.identifier.issn0002-7863
source.periodicalTitleJournal of the American Chemical Society

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