ansa-metallocene derivatives : XXV. Synthesis, crystal structure and reactions of a tetramethylethano-bridged vanadocene dichloride, (CH3)4C2(C5H4)2VCl2

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dc.contributor.authorDorer, Birgitdeu
dc.contributor.authorDiebold, Josefdeu
dc.contributor.authorWeyand, Oliverdeu
dc.contributor.authorBrintzinger, Hans-Herbert
dc.date.accessioned2013-07-31T07:28:49Zdeu
dc.date.available2013-07-31T07:28:49Zdeu
dc.date.issued1992
dc.description.abstractThe tetramethylethano-bridged vanadocene complex (CH3)4C2(C5H4)2VCl2 has been made in two ways: (i) from VCl3·3THF by reaction with (CH3)4C2(C5H4MgCl·2THF)2 in THF and subsequent oxidation with PCl3, and (ii) from VCl4·2THF by reaction with (CH3)4C2(C5H4Li)2 or with (CH3)4C2(C5H4MgCl·2THF)2 in a toluene/dimethoxyethane mixture. Its crystal structure is in accordance with expectations. Reduction of (CH3)4C2(C5H4)2VCl2 with tetrakis(dimethylamino)ethene in toluene or with LiAlH4 in THF yields the monochloride (CH3)4C2(C5H4)2VCl; from this VIII compound cationic complexes (CH3)4C2(C5H4)2VL2+ with L = CO or CNtBu are readily obtained by ligand exchange. 1H NMR signals of these diamagnetic complexes have been assigned to H atoms in α and β C5-ring positions by use of selective nuclear Overhauser effects. The ring-bridged VII complex (CH3)4C2(C5H4)2V could not be prepared. Cyclovoltammetry studies indicate that (in contrast to its unbridged counterpart (C5H5)2V) this VII complex decays within seconds after its formation by electrochemical reduction of its chloro derivatives.eng
dc.description.versionpublished
dc.identifier.citationJournal of Organometallic Chemistry ; 427 (1992), 2. - S. 245-255deu
dc.identifier.doi10.1016/0022-328X(92)83088-Ydeu
dc.identifier.ppn39183259Xdeu
dc.identifier.urihttp://kops.uni-konstanz.de/handle/123456789/23894
dc.language.isoengdeu
dc.legacy.dateIssued2013-07-31deu
dc.rightsterms-of-usedeu
dc.rights.urihttps://rightsstatements.org/page/InC/1.0/deu
dc.subject.ddc540deu
dc.titleansa-metallocene derivatives : XXV. Synthesis, crystal structure and reactions of a tetramethylethano-bridged vanadocene dichloride, (CH<sub>3</sub>)<sub>4</sub>C<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>VCl<sub>2</sub>eng
dc.typeJOURNAL_ARTICLEdeu
dspace.entity.typePublication
kops.citation.bibtex
@article{Dorer1992ansam-23894,
  year={1992},
  doi={10.1016/0022-328X(92)83088-Y},
  title={ansa-metallocene derivatives : XXV. Synthesis, crystal structure and reactions of a tetramethylethano-bridged vanadocene dichloride, (CH<sub>3</sub>)<sub>4</sub>C<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>)<sub>2</sub>VCl<sub>2</sub>},
  number={2},
  volume={427},
  issn={0022-328X},
  journal={Journal of Organometallic Chemistry},
  pages={245--255},
  author={Dorer, Birgit and Diebold, Josef and Weyand, Oliver and Brintzinger, Hans-Herbert}
}
kops.citation.iso690DORER, Birgit, Josef DIEBOLD, Oliver WEYAND, Hans-Herbert BRINTZINGER, 1992. ansa-metallocene derivatives : XXV. Synthesis, crystal structure and reactions of a tetramethylethano-bridged vanadocene dichloride, (CH3)4C2(C5H4)2VCl2. In: Journal of Organometallic Chemistry. 1992, 427(2), pp. 245-255. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(92)83088-Ydeu
kops.citation.iso690DORER, Birgit, Josef DIEBOLD, Oliver WEYAND, Hans-Herbert BRINTZINGER, 1992. ansa-metallocene derivatives : XXV. Synthesis, crystal structure and reactions of a tetramethylethano-bridged vanadocene dichloride, (CH3)4C2(C5H4)2VCl2. In: Journal of Organometallic Chemistry. 1992, 427(2), pp. 245-255. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(92)83088-Yeng
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    <dcterms:title>ansa-metallocene derivatives : XXV. Synthesis, crystal structure and reactions of a tetramethylethano-bridged vanadocene dichloride, (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;VCl&lt;sub&gt;2&lt;/sub&gt;</dcterms:title>
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    <dcterms:abstract xml:lang="eng">The tetramethylethano-bridged vanadocene complex (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;VCl&lt;sub&gt;2&lt;/sub&gt; has been made in two ways: (i) from VCl&lt;sub&gt;3&lt;/sub&gt;·3THF by reaction with (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;MgCl·2THF)&lt;sub&gt;2&lt;/sub&gt; in THF and subsequent oxidation with PCl&lt;sub&gt;3&lt;/sub&gt;, and (ii) from VCl&lt;sub&gt;4&lt;/sub&gt;·2THF by reaction with (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;Li)&lt;sub&gt;2&lt;/sub&gt; or with (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;MgCl·2THF)&lt;sub&gt;2&lt;/sub&gt; in a toluene/dimethoxyethane mixture. Its crystal structure is in accordance with expectations. Reduction of (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;VCl&lt;sub&gt;2&lt;/sub&gt; with tetrakis(dimethylamino)ethene in toluene or with LiAlH&lt;sub&gt;4&lt;/sub&gt; in THF yields the monochloride (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;VCl; from this V&lt;sup&gt;III&lt;/sup&gt; compound cationic complexes (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;VL&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;+&lt;/sup&gt; with L = CO or CN&lt;sup&gt;t&lt;/sup&gt;Bu are readily obtained by ligand exchange. &lt;sup&gt;1&lt;/sup&gt;H NMR signals of these diamagnetic complexes have been assigned to H atoms in α and β C&lt;sub&gt;5&lt;/sub&gt;-ring positions by use of selective nuclear Overhauser effects. The ring-bridged V&lt;sup&gt;II&lt;/sup&gt; complex (CH&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;C&lt;sub&gt;2&lt;/sub&gt;(C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;V could not be prepared. Cyclovoltammetry studies indicate that (in contrast to its unbridged counterpart (C&lt;sub&gt;5&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;V) this V&lt;sup&gt;II&lt;/sup&gt; complex decays within seconds after its formation by electrochemical reduction of its chloro derivatives.</dcterms:abstract>
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kops.description.openAccessopenaccessgreen
kops.identifier.nbnurn:nbn:de:bsz:352-238944deu
kops.sourcefieldJournal of Organometallic Chemistry. 1992, <b>427</b>(2), pp. 245-255. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(92)83088-Ydeu
kops.sourcefield.plainJournal of Organometallic Chemistry. 1992, 427(2), pp. 245-255. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(92)83088-Ydeu
kops.sourcefield.plainJournal of Organometallic Chemistry. 1992, 427(2), pp. 245-255. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(92)83088-Yeng
kops.submitter.emailoleg.kozlov@uni-konstanz.dedeu
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source.bibliographicInfo.fromPage245
source.bibliographicInfo.issue2
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source.bibliographicInfo.volume427
source.identifier.issn0022-328X
source.periodicalTitleJournal of Organometallic Chemistry

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