Alkyl exchange between aluminum trialkyls and zirconocene dichloride complexes : a measure of electron densities at the Zr center

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1998
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Inorganica Chimica Acta. 1998, 270(1-2), pp. 376-381. ISSN 0020-1693. Available under: doi: 10.1016/S0020-1693(97)05871-4
Zusammenfassung

Equilibrium constants have been determined for the formation of 15 different zirconocene monomethyl monochloro complexes from the respective dichloride complexes and Al2(CH3)6. The results indicate that the tendency of a particular zirconocene complex to exchange a chloride against a methyl ligand is a measure for the electron deficiency at its Zr center. The results indicate particularly low electron densities for complexes with indenyl instead of cyclopentadienyl ligands, especially for those containing a dimethylsilyl bridge. Only one methyl group is transferred to a zirconocene dichloride even by a large excess of Al2(CH3)6, while the uptake of two alkyl groups, followed by alkane evolution, is observed with triethyl and triisobutyl aluminum.

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540 Chemie
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Zirconocenes, electron density, aluminum alkyls, methyl transfer
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ISO 690BECK, Stefan, Hans-Herbert BRINTZINGER, 1998. Alkyl exchange between aluminum trialkyls and zirconocene dichloride complexes : a measure of electron densities at the Zr center. In: Inorganica Chimica Acta. 1998, 270(1-2), pp. 376-381. ISSN 0020-1693. Available under: doi: 10.1016/S0020-1693(97)05871-4
BibTex
@article{Beck1998Alkyl-23879,
  year={1998},
  doi={10.1016/S0020-1693(97)05871-4},
  title={Alkyl exchange between aluminum trialkyls and zirconocene dichloride complexes : a measure of electron densities at the Zr center},
  number={1-2},
  volume={270},
  issn={0020-1693},
  journal={Inorganica Chimica Acta},
  pages={376--381},
  author={Beck, Stefan and Brintzinger, Hans-Herbert}
}
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    <dcterms:abstract xml:lang="eng">Equilibrium constants have been determined for the formation of 15 different zirconocene monomethyl monochloro complexes from the respective dichloride complexes and Al&lt;sub&gt;2&lt;/sub&gt;(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;6&lt;/sub&gt;. The results indicate that the tendency of a particular zirconocene complex to exchange a chloride against a methyl ligand is a measure for the electron deficiency at its Zr center. The results indicate particularly low electron densities for complexes with indenyl instead of cyclopentadienyl ligands, especially for those containing a dimethylsilyl bridge. Only one methyl group is transferred to a zirconocene dichloride even by a large excess of Al&lt;sub&gt;2&lt;/sub&gt;(CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;6&lt;/sub&gt;, while the uptake of two alkyl groups, followed by alkane evolution, is observed with triethyl and triisobutyl aluminum.</dcterms:abstract>
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